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WO2005040315A1 - Additive mixture as component of a mineral oil composition - Google Patents

Additive mixture as component of a mineral oil composition Download PDF

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Publication number
WO2005040315A1
WO2005040315A1 PCT/DE2004/002314 DE2004002314W WO2005040315A1 WO 2005040315 A1 WO2005040315 A1 WO 2005040315A1 DE 2004002314 W DE2004002314 W DE 2004002314W WO 2005040315 A1 WO2005040315 A1 WO 2005040315A1
Authority
WO
WIPO (PCT)
Prior art keywords
mineral oil
additive
ethylene
copolymers
mass
Prior art date
Application number
PCT/DE2004/002314
Other languages
German (de)
French (fr)
Inventor
Hiltrud TÄUBERT
Wolfgang Haubold
Torsten Meyer
Erhard Brauer
Dietrich Von Der Wense
Original Assignee
Leuna Polymer Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2003149864 external-priority patent/DE10349864B4/en
Priority claimed from DE2003149865 external-priority patent/DE10349865B4/en
Application filed by Leuna Polymer Gmbh filed Critical Leuna Polymer Gmbh
Priority to KR1020067007765A priority Critical patent/KR100749220B1/en
Priority to CA002542935A priority patent/CA2542935C/en
Priority to EP04790006A priority patent/EP1685216B1/en
Priority to ES04790006T priority patent/ES2402928T3/en
Priority to EA200600804A priority patent/EA011358B1/en
Priority to US10/577,006 priority patent/US7776801B2/en
Priority to JP2006535936A priority patent/JP4991302B2/en
Publication of WO2005040315A1 publication Critical patent/WO2005040315A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
    • C10L2300/30—Mixture of three components

Definitions

  • the invention relates to an additive mixture as part of a formulation of mineral oil as the main component and small proportions of an additive mixture, and to a method for producing a formulation containing the additive mixture from mineral oil.
  • the disadvantages are the inadequate flow behavior and the storage stability of these formulations at low temperatures and the limited lubricity of the formulations if the mineral oil component has a sulfur content of less than 0.005% by mass.
  • the object of the invention is an additive mixture as part of a formulation of mineral oil as the main component and small proportions of an additive mixture, which has an improved flow behavior and an improved shelf life at low temperatures and an improved lubricity. Through the improved Flow behavior is intended to save energy in the pump units, by means of which these formulations are transported.
  • the development of the additive mixtures should take place from the point of view of the use of mineral oils with a very low sulfur content in order to achieve fuels with improved environmental compatibility with regard to the pollutant emissions from vehicles.
  • the object of the invention was achieved by an additive mixture as a constituent of a formulation of mineral oil as the main component and small proportions of an additive mixture, the additive mixture according to the invention containing the additive components a) ethylene-vinyl ester copolymers modified by polar groups with a weight average molecular weight of 3,000 to 50,000 and an ethylene content of 50 to 90% by mass, and b) C -C 6 -oxyalkyl-bridged Ci 2 -C 0 monocarboxylic acids, and / or c) partially and / or completely imidized copolymers of C 4 -Co-ethylenically unsaturated dicarboxylic acid anhydrides and vinyl aromatics and / or CC 36 - ⁇ -0lefinen contain, the content of the additive mixture in the mineral oil 0.005 to 1 mass% and the mass ratio of the additive components a / b or a / c or a / (b + c) is in each case 10:90 to 90:10 ,
  • vinyl ester components which can be contained in the modified ethylene-vinyl ester copolymers are vinyl acetate, vinyl propionate, 2-ethylhexyl vinyl ester, vinyl laurate, 2-hydroxyethyl vinyl ester and 4-hydroxybutyl vinyl ester.
  • the ethylene-vinyl ester copolymers can contain 1 to 30% by mass, based on the vinyl ester, of (meth) acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethylene glycol dimethacrylate or dodecyl acrylate Contain hydroxyethyl methacrylate and / or vinyl ether such as octyl vinyl ether or hexanediol monovinyl ether.
  • acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethylene glycol dimethacrylate or dodecyl acrylate Contain hydroxyethyl methacrylate and / or vinyl ether such as octyl
  • the modification of the ethylene-vinyl ester copolymers by polar groups consists in the incorporation of special end groups such as aldehyde end groups, preferably end groups made of acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde, carboxyalkyl endcap groups, preferably end groups made of mercaptoacetic acid or mercaptopropionic acid, or Alkoxy end groups in the copoly er, in the incorporation of hydroxyl and / or carboxy groups in the copolymer by partial oxidation or saponification, in the reaction of the ethylene-vinyl ester-vinyl alcohol copolymers with aldehydes to form hemiacetals or in the grafting of polar, ethylenically unsaturated Monomer on the copolymer.
  • aldehyde end groups preferably end groups made of acetaldehyde, propionaldehyde, butyral
  • the ethylene-vinyl ester copolymers contained in the additive mixture and modified by polar groups are preferably oxidized ethylene-vinyl acetate copolymers with number average molecular weights from 800 to 5000, acid numbers from 2 to 40 mg KOH / g and OH numbers from 20 to 150 mg KOH / g, or partially saponified ethylene-vinyl acetate copolymers with number average molecular weights of 800 to 5000, in which 5 to 30 mol% of the vinyl acetate units are saponified, or Semi-acetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyraldehyde.
  • hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyraldehyde are hemiacetals of ethylene-vinyl acetate-vinyl alcohol copolymers which, according to DD 295 507 A7, have been reacted with butyraldehyde in a heterogeneous phase.
  • Preferred ethylene-vinyl ester copolymers modified by polar groups are also ethylene-vinyl ester copolymers grafted with 6 to 20% by mass of polar unsaturated monomers of the vinyl ester type, (meth) acrylic ester and / or vinyl ether.
  • the graft modification of these copolymers can be carried out by reaction with the unsaturated monomers in an extruder (DD 282 462 B5) or in a stirred reactor (DD 293 125 B5) in the presence of thermally decomposing radical formers. It is also possible to carry out the modification in the production of the copolymer by the high-pressure process by metering the monomers into the polymer melt in the low-pressure separator or into the discharge extruder.
  • modified ethylene-vinyl ester copolymers are vinyl acetate-grafted ethylene-vinyl acetate copolymers with molar mass numbers of 800 to 5000 and a total vinyl acetate content of 20 to 60 mass%, the vinyl acetate content of the copolymer backbone chain 10 to 40 mass% and that The proportion of the grafted vinyl acetate side chains is 10 to 20% by mass.
  • the modified ethylene-vinyl ester copolymers can contain up to 35 pigments of poly-C 6 -C 36 -alkyl- (eth) acrylates and / or unmodified ethylene-vinyl ester copolymers.
  • polyalcohols that oxyalkyl-bridged as the alcohol component in the C 2 -C 6 C ⁇ 2 -Co-monocarboxylic acids b) are contained the additive mixture are ethylene glycol, polyalkylene glycols, glycerol, 1, 1, 1-tris (hydroxymethyl) - propane, pentaerythritol and sorbitol.
  • C 2 -C 40 monocarboxylic acids which are present as a carboxylic acid component in the CC 6 -oxyalkyl-bridged C 2 -C 40 monocarboxylic acids b) of the additive mixture are lauric acid, palmitic acid, stearic acid, oleic acid, elaidic acid, ricinoleic acid, Eleostearic acid, linoleic acid, linolenic acid and erucic acid, or dimer acids based on oleic acid or linolenic acid.
  • C 2 -C 6 -oxyalkyl-bridged C 2 -C 4 o-monocarboxylic acids b) are also mixed esters of polyalcohols in which the polyalcohols are esterified by mixtures of C 2 -C 40 monocarboxylic acids.
  • Specific examples of C 2 -C 6 -oxyalkyl-bridged Ci 2 -C 4 o-monocarboxylic acids are the monoester of ethylene glycol with dilinolenic acid, a C 36 ⁇ dimer acid, the diester of propylene glycol with oleic acid and the triester of pentaerythritol with stearic acid.
  • C 2 -C 6 -oxyalkyl-bridged C 2 -C 40 monocarboxylic acids b) are esters of unsaturated C 16 -C 24 monocarboxylic acids with C 3 -C 4 polyalcohols, the proportion of C 2 2 -monocarboxylic acids based on the total se the C ⁇ 6 -C 24 monocarboxylic acids, 45 to 52 mass%.
  • Examples of unsaturated Ci 6 -C 24 monocarboxylic acids which may be contained in the preferred esters of unsaturated C 6 -C 2 4 monocarboxylic acids with C 3 -C 4 polyalcohols as additive component b) are oleic acid, linoleic acid, linolenic acid and erucic acid.
  • Examples of ethylenically unsaturated C 4 -C 2 o _ dicarboxylic acid anhydrides as the monomeric component of the copoly mers of ethylenically unsaturated C 4 -C 2 o-dicarboxylic acid and anhydrides 01efinen - ⁇ -vinyl aromatics and / or C 2 -C 36 Partially and / or completely imidized in the additive mixture of the mineral oil formulations as additive component c) are allylsuccinic anhydride, bicyclo-heptenedicarboxylic anhydride, bicyclooctenedicarboxylic anhydride, carbomethoxymaleinic anhydride, dicarbonic acid anhydride, diconic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid
  • Suitable vinyl aromatic compounds as comonomers as monomer components in the partially and / or fully imidized copolymers of ethylenically unsaturated C 4 _ -C2o dicarboxylic anhydrides c) the Additivmi- mixtures can be included are styrene, ⁇ -methyl styrene and vinyl pyridine.
  • Examples of suitable C 2 -C 36 - -01efins as comonomers which may be present as monomer components in the partially and / or completely imidized copolymers of ethylenically unsaturated C 4 -C 20 dicarboxylic anhydrides c) of the additive mixtures are ethylenically unsaturated monomers of the type C 2 -C 2 o-olefins, C 4 -C 2 ⁇ - acrylic acid esters, C 5 -C 22 methacrylic acid esters, C 5 -C ⁇ 4 -vinyl silanes, C 6 -C 5 -acrylatesilanes, acrylic acid, methacrylic acid, Acrylonitrile, vinyl oxazoline, isopropenyloxazoline, vinyl pyrrolidone, amino-C 8 -C 8 -alkyl- (meth) acrylates, C 3 -C 2 o-vinyl esters, C 3 -C 2 o-vin
  • Preferred comonomers as monomer components in the partially and / or completely imidized copolymers of ethylenically unsaturated C 4 -C 2 o-dicarboxylic acid anhydrides c) of the additive mixtures are isobutylene, diisobutylene, vinyl acetate, styrene and ⁇ -methylstyrene.
  • the partially imidized copolymers of C 4 -C 2 o-ethylenically unsaturated acid anhydrides and vinyl aromatics and / or C 2 -C 36 - 01efins as additive component c) preferably have a molar ratio of 1: 1 to 1: 9 and molar mass weight average of 5000 to 500,000, in which the partial imidization with ammonia, C 1 -C 24 monoalkylamines, C 5 -Ci 8 aromatic monoamines, C 2 -Ci 8 monoalcohols, monoaminated poly (C 2 -C 4 alkylene) oxides a molecular weight of 400 to 3000, and / or mono-retarded poly (C 2 -C 4 alkylene) oxides of a molecular weight of 100 to 10000, the molar ratio of anhydride groups copolymer / ammonia, amino groups C 1 -C 24 monoalkylamines, Cg-Cis-aromatic monoamines
  • Particularly suitable as partially imidized copolymers of ethylenically unsaturated C 4 -co-dicarboxylic acid anhydrides c) are with C 1 -C 24 -monoalkylamines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine or eico-sylain, monosubstituted diamines of the type N-dodecyl-1,3-diaminopropane, N-octadecyl-1,3-diaminopropane or N-octadecylpropylenetriamine or amino alcohols such as aminodecan-10-ol or aminohexadecan-16-ol imidized maleic anhydride copolymers.
  • C 1 -C 24 -monoalkylamines such as oleylamine, dodecylamine, hexadecylamine,
  • the partially imidized copolymers of unsaturated dicarboxylic anhydrides and vinyl aromatics and / or C 2 -C 3 6- ⁇ -olefins as additive component c) are particularly preferably maleic anhydride- ⁇ -methylstyrene copolymers partially imidized with Ce-C 24 monoalkylamines, in which the molar ratio of anhydride groups in the copolymer / bound C 6 -C 24 -monoalkylamine in the copolymer is 8: 1 to 1.3: 1.
  • mineral oils which form the main component in the recipes from mineral oil and small proportions of an additive mixture, are crude oils and petroleum distillates with a boiling range from 100 to 500 ° C such as lubricating oils, kerosene, diesel, heating oil, heavy heating oils, petroleum, Tractor fuel and cracked gasoline.
  • the mineral oils can also contain up to 30 mass% synthetic hydrocarbons from the Fischer-Tropsch synthesis, up to 20 mass% modified vegetable oils based on sunflower oil, soybean oil, rapeseed oil, or oils of animal origin, biodiesel and / or up to 10 mass% alcohols such as methanol or ethanol contain.
  • the mineral oils in the formulations of mineral oil and small proportions of an additive mixture are preferred crude oils or fuel oils from a middle distillate with a sulfur content below 0.05% by mass, in particular heating oils, gas oils or diesel oils.
  • the preferred content of the additive mixture in the mineral oil is 0.01 to 0.3% by mass.
  • the mineral oil can also contain a total of 0 to 200% by mass, based on the sum of additive components a) and b) or a) and c) or a), b) and c), of further additive components of the fatty acid mixture type, polar nitrogen compounds, preferably polyamines, ether amines, amino alcohols, amine salts, amides or imides of polyvalent carboxylic acids; C 7 -C 3 o-alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, unmodified ethylene-vinyl ester copolymers, hydrocarbon polymers, alkylphenol-aldehyde copolymers, aromatic compounds with Cs-Cioo-alkyl substituents, carboxylated polyamines, detergents, corrosion inhibitors, Contain demulsifiers, metal deactivators, cetane improvers, defoamers and / or cosolvents.
  • polar nitrogen compounds preferably polyamine
  • fatty acid mixtures contained in the mineral oil as further additive components are mixtures of saturated and / or unsaturated C 6 -C 40 carboxylic acids such as lauric acid, palmitic acid, oleic acid, linolenic acid, di-fatty acids and alkenyl succinic acids.
  • Examples of the polar nitrogen compounds of the type contained in the mineral oil as further additive components Polyamines are N-hexadecyl-1, 3-diaminopropane, N-octadecyldipropylenetriamine, N-dodecyl-1, 3-diaminopropane, N, N'-didodecyl-1, 3-diaminopropane and N, N '-dioctadecyldipropylenentriamine.
  • Examples of the polar nitrogen compounds of the etheramine type contained in the mineral oil as further additive components are 3-methoxypropylamine, 3-N-octyloxypropyl-1, 3-diaminopropane and 3-N- (2, 4, 6-trimethyldecyloxypropyl) -1, 3 -diaminopropan.
  • Examples of the polar nitrogen compounds of the amino alcohol type contained in the mineral oil as further additive components are aminopentan-5-ol, aminoundecan-11-ol and 2-amino-2-methylpropanol.
  • Examples of the amines on which the polar nitrogen compounds of the type amine salts, amides or imides of polyvalent carboxylic acids are based as further additive components are C 8 -C 4 o-amines such as hydrogenated tallamine, tetra-decylamine, eicosylamine, dioctadecylamine, methylbehenylamine, N-oleyl -1, 3-diaminopropane, N-stearyl-l-methyl-1,3-diaminopropane or N-oleyldipropylenetriamine.
  • C 8 -C 4 o-amines such as hydrogenated tallamine, tetra-decylamine, eicosylamine, dioctadecylamine, methylbehenylamine, N-oleyl -1, 3-diaminopropane, N-stearyl-l-methyl-1,3-diaminopropane or N-oleyldi
  • polyvalent carboxylic acids on which the polar nitrogen compounds of the type amine salts or amides of polyvalent carboxylic acids are based as further additive components are phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, ethylenediaminetetraacetic acid and cyclohexanedicarboxylic acid.
  • Amine salts are N-methyl-triethanolammonium disearyl ester chloride and N-methyltriethanolammonium disearyl ester methosulfate.
  • C 7 -C 30 alcohols which may be contained in the mineral oil as further additive components are dodecanol, stearyl alcohol and ceryl alcohol.
  • polyalkylene glycols which may be present in the mineral oil as further additive components are polyethylene glycols, polypropylene glycols and ethylene oxide / propylene oxide copolymers with molecular weights from 500 to 5000.
  • esters of polyoxyalkylene compounds which may be contained in the mineral oil as further additive components are C 0 -C 24 -monoalkyl esters or dialkyl esters of polyalkylene glycols such as polyethylene glycol monostearyl ester or polypropylene glycol dioleate.
  • ethers of polyoxyalkylene compounds which may be present in the mineral oil as further additive components are C 1 -C 4 -monoalkyl ethers or dialkyl ethers of polyalkylene glycols such as polyethylene glycol monomethyl ether or polypropylene glycol dibutyl ether.
  • hydrocarbon polymers which may be contained in the mineral oil as further additive components are copolymers of ethylene and C 3 -C 20 - olefins such as ethylene-propylene copolymers or ethylene-dodecene copolymers or hydrogenated polymers of polyunsaturated monomers of the type hydrogenated diene copolymers such as hydrogenated polybutadiene or hydrogenated polyisoprene with number average molecular weights up to 30,000.
  • alkylphenol-aldehyde copolymers which may be present in the mineral oil as further additive components are copolymers which can be prepared by reacting alkylated phenols such as phenol-propylene oligomer adducts with paraformaldehyde.
  • aromatic compounds having C 8 -C ⁇ 0 o- alkyl substituents which may be contained as other additive components in mineral oil, are compounds which are halogenated by Friedel-Crafts condensation hydrocarbons such as halogenated polyethylene wax with aromatic hydrocarbons such as benzene or naphthalene may be prepared.
  • detergents which may be present in the mineral oil as further additive components are aliphatic sulfonic acids such as Cs-C 3 o-alkanesulfonates or aromatic-aliphatic alkanesulfonates, in particular nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid and nonylnaphthalenesulfonic acid.
  • aliphatic sulfonic acids such as Cs-C 3 o-alkanesulfonates or aromatic-aliphatic alkanesulfonates
  • nonylbenzenesulfonic acid dodecylbenzenesulfonic acid
  • didodecylbenzenesulfonic acid didodecylbenzenesulfonic acid and nonylnaphthalenesulfonic acid.
  • demulsifiers which may be present in the mineral oil as further additive components are oxyalkylated phenol-formaldehyde condensates, polyalkylene glycol-modified diglycidyl ethers, polyesteramines or alkoxylated fatty acids.
  • cetane improvers which may be present in the mineral oil as further additive components are organic nitric acid esters such as ethylhexyl nitrate, cyclohexyl nitrate or ethoxyethyl nitrate, or soluble organic peroxides, hydroperoxides or peresters.
  • Preferred defoamers, which may be contained in the mineral oil as further additive components, are polyalkylene oxide-siloxane block copolymers and carboxylated polyamines.
  • polyalkylene oxide-siloxane block copolymers are block copolymers which contain a combination of trifunctional siloxane blocks such as monomethylsiloxane groups, difunctional siloxane groups such as dimethylsiloxane groups and monofunctional siloxane groups such as trimethylsiloxane groups, a preferred length of the siloxane units being 5 bis 20 siloxane blocks.
  • the preferred length is 2 to 40 monomer units; polyoxyalkylene blocks composed of ethylene oxide and / or propylene oxide units are preferred.
  • carboxylated polyamines as defoamers are reaction products of C 8 -C 24 fatty acids and amines such as ethylenediamine, butylenediamine, diethylenetriamine and pentaethylenehexamine-1,2-diaminobutanol.
  • cosolvents which can be contained in the mineral oil compositions as further additive components are gasoline fractions, toluene, xylene, ethylbenzene, isononanol, ethylhexanol, dodecylphenol, epoxidized rapeseed oil and epoxidized soybean oil.
  • the formulations made from mineral oil as the main component and low proportions of an additive mixture are produced by a process in which, according to the invention, formulations containing the additive components a) ethylene-vinyl ester copolymers modified by polar groups with molecular weights of 3000 to 50,000 and an ethylene content of 50 to 90% by mass, and b) C 2 -C 6 -oxyalkyl-bridged C 2 -C 40 monocarboxylic acids, and / or c) contain partially and / or completely imidized copolymers of C 4 -C 2 o-unsaturated dicarboxylic acid anhydrides and vinyl aromatics and / or C 2 -C 35 - ⁇ -01efins, the content of the additive mixture in the mineral oil being 0.005 to 1% by mass and the mass ratio of the additive components a / b or a / c or a / (b + c) 10: 90 to 90: 10, are prepared by a pre-homogenization process in which
  • formulations of mineral oil as the main component and small proportions of an additive mixture according to the invention are preferred as being too low at low portable flowable media and suitable as mineral oil fuel with high lubrication and flowability.
  • Examples of the flowable media to be transported at low temperatures are the transportation of crude oil formulations from the crude oil production site through pipelines for loading and storage, and the transportation of diesel or heating oil formulations in pipelines.
  • Vinyl acetate content modified method according to ISO 8995, DIN 16778 part 2: 2 g sample are weighed to the nearest 0.001 g and in a 300 ml Erlenmeyer flask with 70 ml distilled xylene and 2 boiling pearls approx. Solved for 15 min while heating the reflux condenser. Then approx. 30 ml of ethanol are slowly added through the reflux condenser, the Erlenmeyer flask is removed from the hotplate, 30 ml of ethanol, 0.5 N KOH from the burette and 2 boiling pearls are added, and the sample is refluxed for 1 h.
  • V consumption in ml of 0.5 N ethanolic KOH for the sample
  • B consumption in ml of 0.5 N ethanolic KOH for the blank value
  • Lubricity test (corrected "wear scar diameter” at 60 ° C) according to ISO 12156-1
  • a 500 ml sample is stored in a measuring cylinder for 16 h and then the 80% by volume of the sample above is sucked off and discarded. The remaining 20 vol% of the sample (100 ml) are homogenized at 40 ° C and the cloud point (CP) is determined according to DIN EN 23 015.
  • a 500 ml mineral oil sample is shaken 20 times vertically, temperature-controlled at 10 ° C. for 16 h, shaken 10 times vertically, and the entire sample is passed through a filter made of cellulose nitrate (diameter 50 mm, pore size 0.8 ⁇ m) on a suction cup with a vacuum of approx. 200 hPa is applied, filtered. The time (s) during which the sample runs through the filter is determined. The SEDAB filtration test is passed if the sample passes the filter within a period of ⁇ 120 s. example 1
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • the additive solution according to 1.2 is injected into a product stream of non-additized diesel batch 16080601 at 800 kg / min at 0.48 kg / min and transferred to a storage tank.
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • Styrene-maleic anhydride copolymer partially imidized with Ci 6 -C 8 fatty amine, average molecular weight 21000 g / mol, acid number 37
  • Vinyl acetate-ethylhexyl acrylate copolymer (molar ratio 1.5: 1, molar mass number average 13500)
  • the additive solution according to 2.2 is injected into a product stream of non-additized Diesel Charge 030210 at 800 kg / min at 0.12 kg / min and transferred to a storage tank.
  • the CFPP value is -5 ° C and the "wear scar diameter" is 528 ⁇ m.
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • Styrene-maleic anhydride copolymer partially imidized with Ci 6 -C 8 fatty amine, average molecular weight 9500 g / mol, acid number 25
  • the additive solution according to 3.2 is injected into a product stream of non-additized heating oil batch 030225 at 800 kg / min at 0.24 kg / min and transferred to a storage tank.
  • the CFPP value is -13 ° C.
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • the additive solution according to 4.2 is injected into a product stream of non-additized heating oil batch 030218 at 800 kg / min at 0.28 kg / min and transferred to a storage tank.
  • the CFPP value is -1 ° C.
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • Styrene-maleic anhydride copolymer partially imidized with -C 6 -C 8 fatty amine, number average molecular weight 26500 g / mol, acid number 8.2
  • the additive solution according to 5.2 is injected into a product stream of non-additized diesel batch 16080601 at 800 kg / min at 0.48 kg / min and transferred to a storage tank. Testing the cold resistance of the mineral oil formulation gives a CFPP value of -17 ° C.
  • the CP value of the short-term sediment test is + 6 ° C.
  • the SEDAB filtration test is passed (500 ml in 75 s). If a mineral oil formulation is produced under the same conditions that contains only the non-grafted copolymer wax as an additive, the CFPP value is -3 ° C.
  • the CP value of the short-term sediment test is + 10 ° C.
  • the SEDAB filtration test is considered failed (468 ml in> 120 s).
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • Octadecen-maleic anhydride copolymer partially imidized with Ci 6 -C ⁇ 8 - fatty amine, acid number 40, number average molar mass 4200 g / mol,
  • the additive solution according to 6.2 is injected into a product stream of non-additized Diesel Charge 030210 at 800 kg / min at 0.24 kg / min and transferred to a storage tank.
  • Example 7 Testing the cold resistance of the mineral oil formulation gives a CFPP value of -7 ° C.
  • the CP value of the short-term sediment test is + 8 ° C.
  • the SEDAB filtration test is passed (500 ml in 82 s). If a mineral oil formulation is produced under the same conditions that contains only the non-saponified copolymer wax as an additive, the CFPP value is -5 ° C.
  • the CP value of the short-term sediment test is + 12 ° C.
  • the SEDAB filtration test is considered failed (468 ml in> 120 s).
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • the additive solution according to 7.2 is injected into a product stream of non-additized Diesel Charge 030225 at 800 kg / min at 0.24 kg / min and transferred to a storage tank.
  • the CFPP value is -13 ° C.
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • the additive solution according to 8.2 is injected into a product stream of non-additized diesel batch 16080601 at 800 kg / min at 0.48 kg / min and transferred to a storage tank.
  • the CFPP value is -3 ° C.

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Abstract

An additive mixture as component of a mineral oil composition comprises, as main components and trace proportions of the additive mixture, the following additive components: a) ethylene vinyl ester copolymers modified with polar groups with molecular mass weight averages of 3,000 to 50,000 and an ethylene component of 50 to 90 mass %, b) C12-C40 monocarboxylic acids with C2-C6 oxyalkyl bridges and/or c) partly and/or completely imidated copolymers of unsaturated C4-C20 dicarboxylic anhydrides and vinyl aromatics and/or C2-C36 alpha -olefins, whereby the content of the additive mixture in the mineral oil is 0.005 to 1 mass %. The compositions are suitable for low temperature flowing media and high lubricity mineral oil fuels of high ease of flow.

Description

Additivmischung als Bestandteil einer Rezeptur aus Mineralöl Additive mixture as part of a mineral oil recipe
BESCHREIBUNGDESCRIPTION
Die Erfindung betrifft eine Additivmischung als Bestandteil einer Rezeptur aus Mineralöl als Hauptkomponente und geringen Anteilen einer Additivmischung sowie ein Verfahren zur Herstellung einer die Additivmischung enthalten- den Rezeptur aus Mineralöl.The invention relates to an additive mixture as part of a formulation of mineral oil as the main component and small proportions of an additive mixture, and to a method for producing a formulation containing the additive mixture from mineral oil.
Rezepturen aus Mineralölen als Hauptkomponente und geringen Anteilen von Additivmischungen aus üblichen nichtmo- difizierten Ethylen-Vinylacetat-Copolymeren, Kohlenwas- serstoffpolymeren, veresterten Maleinsäureanhydrid-Ole- fin-Copolymeren, polaren StickstoffVerbindungen wie Amin- salze von mehrwertigen Carbonsäuren und veresterten Poly- oxyalkylenen sind bekannt (WO 94/10 267 AI, WO 95/33 012 AI, EP 0 921 183 AI, WO 93/14 178 AI, EP 0 889 323 AI) .Recipes made from mineral oils as the main component and small proportions of additive mixtures made from customary unmodified ethylene-vinyl acetate copolymers, hydrocarbon polymers, esterified maleic anhydride-olefin copolymers, polar nitrogen compounds such as amine salts of polyvalent carboxylic acids and esterified polyoxyalkylenes are known (WO 94/10 267 AI, WO 95/33 012 AI, EP 0 921 183 AI, WO 93/14 178 AI, EP 0 889 323 AI).
Von Nachteil sind das unzureichende Fliessverhalten und die Lagerbeständigkeit dieser Rezepturen bei niedrigen Temperaturen und die begrenzte Schmierfähigkeit der Rezepturen, wenn die Mineralölkomponente einen Schwefelge- halt unter 0,005 Masse% besitzt.The disadvantages are the inadequate flow behavior and the storage stability of these formulations at low temperatures and the limited lubricity of the formulations if the mineral oil component has a sulfur content of less than 0.005% by mass.
Aufgabe der Erfindung ist eine Additivmischung als Bestandteil einer Rezeptur aus Mineralöl als Hauptkomponente und geringen Anteilen einer Additivmischung, die ein verbessertes Fliessverhalten und eine verbesserte Lagerbeständigkeit bei niedrigen Temperaturen und eine verbesserte Schmierfähigkeit besitzt. Durch das verbesserte Fliessverhalten soll eine Energieeinsparung bei den Pumpenaggregaten erreicht werden, durch die der Transport dieser Rezepturen erfolgt. Die Entwicklung der Additivmischungen soll unter dem Gesichtspunkt des Einsatzes von Mineralölen mit sehr niedrigem Schwefelgehalt erfolgen, um Treibstoffe verbesserter Umweltverträglichkeit hinsichtlich der Schadstoffemission von Fahrzeugen zu erzielen.The object of the invention is an additive mixture as part of a formulation of mineral oil as the main component and small proportions of an additive mixture, which has an improved flow behavior and an improved shelf life at low temperatures and an improved lubricity. Through the improved Flow behavior is intended to save energy in the pump units, by means of which these formulations are transported. The development of the additive mixtures should take place from the point of view of the use of mineral oils with a very low sulfur content in order to achieve fuels with improved environmental compatibility with regard to the pollutant emissions from vehicles.
Die Aufgabe der Erfindung wurde durch eine Additivmischung als Bestandteil einer Rezeptur aus Mineralöl als Hauptkomponente und geringen Anteilen einer Additivmischung gelöst, wobei die Additivmischung erfindungsgemäß die Additivkomponenten a) durch polare Gruppen modifizierte Ethylen-Vinylester- Copolymere mit Molmassengewichtsmitteln von 3000 bis 50000 und einem Ethylenanteil von 50 bis 90 Masse%, und b) C -C6-oxyalkylverbrückte Ci2-C0-Monocarbonsäuren, und/oder c) partiell und/oder vollständig imidisierte Copolymere aus C4-Co-ethylenisch ungesättigten Dicarbonsäureanhydri- den und Vinylaromaten und/oder C-C36-α-0lefinen enthalten, wobei der Gehalt der Additivmischung im Mineralöl 0,005 bis 1 Masse% und das Masseverhältnis der Additivkomponenten a/b oder a/c oder a/(b+c) jeweils 10 : 90 bis 90 : 10 beträgt.The object of the invention was achieved by an additive mixture as a constituent of a formulation of mineral oil as the main component and small proportions of an additive mixture, the additive mixture according to the invention containing the additive components a) ethylene-vinyl ester copolymers modified by polar groups with a weight average molecular weight of 3,000 to 50,000 and an ethylene content of 50 to 90% by mass, and b) C -C 6 -oxyalkyl-bridged Ci 2 -C 0 monocarboxylic acids, and / or c) partially and / or completely imidized copolymers of C 4 -Co-ethylenically unsaturated dicarboxylic acid anhydrides and vinyl aromatics and / or CC 36 -α-0lefinen contain, the content of the additive mixture in the mineral oil 0.005 to 1 mass% and the mass ratio of the additive components a / b or a / c or a / (b + c) is in each case 10:90 to 90:10 ,
Beispiele für die Vinylesterkomponenten, die in den modifizierten Ethylen-Vinylester-Copolymeren enthalten sein können, sind Vinylacetat, Vinylpropionat, 2-Ethylhexyl- vinylester, Vinyllaurat, 2-Hydroxyethylvinylester und 4- Hydroxybutylvinylester .Examples of the vinyl ester components which can be contained in the modified ethylene-vinyl ester copolymers are vinyl acetate, vinyl propionate, 2-ethylhexyl vinyl ester, vinyl laurate, 2-hydroxyethyl vinyl ester and 4-hydroxybutyl vinyl ester.
Die Ethylen-Vinylester-Copolymere können als weitere un- gesättigte Esterkomponenten 1 bis 30 Masse%, bezogen auf den Vinylester, (Meth) acrylsäureester wie Acrylsäureme- thylester, Methylmethacrylat , Ethyl ethacrylat, Butylac- rylat, 2-Ethylhexylacrylat , Ethylenglycoldimethacrylat , Dodecylacrylat oder Hydroxyethylmethacrylat und/oder Vi- nylether wie Octylvinylether oder Hexandiolmonovinylether enthalten.As further unsaturated ester components, the ethylene-vinyl ester copolymers can contain 1 to 30% by mass, based on the vinyl ester, of (meth) acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethylene glycol dimethacrylate or dodecyl acrylate Contain hydroxyethyl methacrylate and / or vinyl ether such as octyl vinyl ether or hexanediol monovinyl ether.
Die Modifizierung der Ethylen-Vinylester-Copolymere durch polare Gruppen besteht in dem Einbau spezieller Endgrup- pen wie Aldehyd-Endgruppen, bevorzugt Endgruppen aus Ace- taldehyd, Propionaldehyd, Butyraldehyd oder Isobutyralde- hyd, Carboxyalkyl ercaptoendgruppen, bevorzugt Endgruppen aus Mercaptoessigsäure oder Mercaptopropionsäure, oder Alkoxyendgruppen in das Copoly er, in dem Einbau von Hydroxy- und/oder Carboxygruppen in das Copolymer durch partielle Oxidation oder Verseifung, in der Umsetzung der Ethylen-Vinylester-Vinylalkohol-Copolymeren mit Aldehyden zu Halbacetalen oder in der AufPfropfung polarer, ethyle- nisch ungesättigter Monomerer auf das Copolymer.The modification of the ethylene-vinyl ester copolymers by polar groups consists in the incorporation of special end groups such as aldehyde end groups, preferably end groups made of acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde, carboxyalkyl endcap groups, preferably end groups made of mercaptoacetic acid or mercaptopropionic acid, or Alkoxy end groups in the copoly er, in the incorporation of hydroxyl and / or carboxy groups in the copolymer by partial oxidation or saponification, in the reaction of the ethylene-vinyl ester-vinyl alcohol copolymers with aldehydes to form hemiacetals or in the grafting of polar, ethylenically unsaturated Monomer on the copolymer.
Die in der Additivmischung enthaltenen durch polare Gruppen modifizierten Ethylen-Vinylester-Copolymere sind bevorzugt oxidierte Ethylen-Vinylacetat-Copolymere mit Molmassen-Zahlenmitteln von 800 bis 5000, Säurezahlen von 2 bis 40 mg KOH/g und OH-Zahlen von 20 bis 150 mg KOH/g, oder teilverseifte Ethylen-Vinylacetat-Copolymere mit Molmassen-Zahlenmitteln von 800 bis 5000, bei denen 5 bis 30 Mol% der Vinylacetateinheiten verseift vorliegen, oder Halbacetale von Ethylen-Vinylester-Vinylalkohol-Copolyme- ren mit Butyraldehyd.The ethylene-vinyl ester copolymers contained in the additive mixture and modified by polar groups are preferably oxidized ethylene-vinyl acetate copolymers with number average molecular weights from 800 to 5000, acid numbers from 2 to 40 mg KOH / g and OH numbers from 20 to 150 mg KOH / g, or partially saponified ethylene-vinyl acetate copolymers with number average molecular weights of 800 to 5000, in which 5 to 30 mol% of the vinyl acetate units are saponified, or Semi-acetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyraldehyde.
Beispiele für Halbacetale von Ethylen-Vinylester-Vinylal- kohol-Copolymeren mit Butyraldehyd sind Halbacetale von Ethylen-Vinylacetat-Vinylalkohol-Copolymeren, die nach DD 295 507 A7 in heterogener Phase mit Butyraldehyd umgesetzt worden sind.Examples of hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyraldehyde are hemiacetals of ethylene-vinyl acetate-vinyl alcohol copolymers which, according to DD 295 507 A7, have been reacted with butyraldehyde in a heterogeneous phase.
Bevorzugt als durch polare Gruppen modifizierte Ethylen- Vinylester-Copolymere sind ebenfalls mit 6 bis 20 Masse% polaren ungesättigten Monomeren vom Typ Vinylester, (Meth) acrylester und/oder Vinylether gepfropfte Ethylen- Vinylester-Copolymere .Preferred ethylene-vinyl ester copolymers modified by polar groups are also ethylene-vinyl ester copolymers grafted with 6 to 20% by mass of polar unsaturated monomers of the vinyl ester type, (meth) acrylic ester and / or vinyl ether.
Die Pfropfmodifizierung dieser Copolymeren kann durch Umsetzung mit den ungesättigten Monomeren im Extruder (DD 282 462 B5) oder im Rührreaktor (DD 293 125 B5) in Gegenwart von thermisch zerfallenden Radikalbildnern durchge- führt werden. Möglich ist ebenfalls, die Modifizierung bei der Herstellung des Copolymers nach dem Hochdruckverfahren durch Eindosierung der Monomeren in die Polymerschmelze im Niederdruckabscheider oder in den Austragsextruder vorzunehmen.The graft modification of these copolymers can be carried out by reaction with the unsaturated monomers in an extruder (DD 282 462 B5) or in a stirred reactor (DD 293 125 B5) in the presence of thermally decomposing radical formers. It is also possible to carry out the modification in the production of the copolymer by the high-pressure process by metering the monomers into the polymer melt in the low-pressure separator or into the discharge extruder.
Besonders bevorzugt als modifizierte Ethylen-Vinylester- Copolymere sind mit Vinylacetat gepfropfte Ethylen-Vinylacetat-Copolymere mit Molmassenzahlenmitteln von 800 bis 5000 und einem Gesamtvinylacetatgehalt von 20 bis 60 Mas- se%, wobei der Vinylacetatgehalt der Copolymerrückgrat- kette 10 bis 40 Masse% und der Anteil der aufgepfropften Vinylacetat-Seitenketten 10 bis 20 Masse% beträgt. Die modifizierten Ethylen-Vinylester-Copolymere können bis 35 Massel Poly-C6-C36-alkyl- ( eth) acrylate und/oder nichtmodifizierte Ethylen-Vinylester-Copolymere enthalten.Particularly preferred as modified ethylene-vinyl ester copolymers are vinyl acetate-grafted ethylene-vinyl acetate copolymers with molar mass numbers of 800 to 5000 and a total vinyl acetate content of 20 to 60 mass%, the vinyl acetate content of the copolymer backbone chain 10 to 40 mass% and that The proportion of the grafted vinyl acetate side chains is 10 to 20% by mass. The modified ethylene-vinyl ester copolymers can contain up to 35 pigments of poly-C 6 -C 36 -alkyl- (eth) acrylates and / or unmodified ethylene-vinyl ester copolymers.
Beispiele für Polyalkohole, die als Alkoholkomponente in den C2-C6-oxyalkyl-verbrückten Cι2-Co-Monocarbonsäuren b) der Additivmischung enthalten sind, sind Ethylenglycol, Polyalkylenglycole, Glycerin, 1, 1, 1-Tris- (hydroxymethyl) - propan, Pentaerythrit und Sorbit.Examples of polyalcohols that oxyalkyl-bridged as the alcohol component in the C 2 -C 6 Cι 2 -Co-monocarboxylic acids b) are contained the additive mixture are ethylene glycol, polyalkylene glycols, glycerol, 1, 1, 1-tris (hydroxymethyl) - propane, pentaerythritol and sorbitol.
Beispiele für Cι2-C40-Monocarbonsäuren, die als Carbonsäurekomponente in den C-C6-oxyalkylverbrückten Cι2-C40-Mono- carbonsäuren b) der Additivmischung enthalten sind, sind Laurinsäure, Palmitinsäure, Stearinsäure, Ölsäure, Elai- dinsäure, Ricinolsäure, Eleostearinsäure, Linolsäure, Li- nolensäure und Erucasäure, oder Dimersäuren auf Basis Ölsäure oder Linolensäure.Examples of C 2 -C 40 monocarboxylic acids which are present as a carboxylic acid component in the CC 6 -oxyalkyl-bridged C 2 -C 40 monocarboxylic acids b) of the additive mixture are lauric acid, palmitic acid, stearic acid, oleic acid, elaidic acid, ricinoleic acid, Eleostearic acid, linoleic acid, linolenic acid and erucic acid, or dimer acids based on oleic acid or linolenic acid.
Bevorzugt werden als C2-C6-oxyalkylverbrückte Cι2-C4o-Mono- carbonsäuren b) ebenfalls Mischester von Polyalkoholen, bei denen die Polyalkohole durch Mischungen von Cι2-C40- Monocarbonsäuren verestert sind. Spezielle Beispiele für C2-C6-oxyalkylverbrückte Ci2-C4o-Monocarbonsäuren sind der Monoester von Ethylenglycol mit Dilinolensäure, einer C36~Dimersäure, der Diester von Propy-lenglycol mit Ölsäure und der Triester von Pentaerythrit mit Stearinsäure .Preferred C 2 -C 6 -oxyalkyl-bridged C 2 -C 4 o-monocarboxylic acids b) are also mixed esters of polyalcohols in which the polyalcohols are esterified by mixtures of C 2 -C 40 monocarboxylic acids. Specific examples of C 2 -C 6 -oxyalkyl-bridged Ci 2 -C 4 o-monocarboxylic acids are the monoester of ethylene glycol with dilinolenic acid, a C 36 ~ dimer acid, the diester of propylene glycol with oleic acid and the triester of pentaerythritol with stearic acid.
Besonders bevorzugt als C2-C6-oxyalkylverbrückte Cι2-C40- Monocarbonsäuren b) sind Ester von ungesättigten C16-C24- Monocarbonsäuren mit C3-C4-Polyalkoholen, wobei der Anteil von C22-Monocarbonsäuren, bezogen auf die Gesamtmas- se der Cι6-C24 Monocarbonsäuren, 45 bis 52 Masse% beträgt .Particularly preferred as C 2 -C 6 -oxyalkyl-bridged C 2 -C 40 monocarboxylic acids b) are esters of unsaturated C 16 -C 24 monocarboxylic acids with C 3 -C 4 polyalcohols, the proportion of C 2 2 -monocarboxylic acids based on the total se the Cι 6 -C 24 monocarboxylic acids, 45 to 52 mass%.
Beispiele für ungesättigte Ci6-C24-Monocarbonsäuren, die in den bevorzugten Estern von ungesättigten Cι6-C24- Monocarbonsäuren mit C3-C4-Polyalkoholen als Additivkomponente b) enthalten sein können, sind Ölsäure, Linolsäu- re, Linolensäure und Erucasäure.Examples of unsaturated Ci 6 -C 24 monocarboxylic acids which may be contained in the preferred esters of unsaturated C 6 -C 2 4 monocarboxylic acids with C 3 -C 4 polyalcohols as additive component b) are oleic acid, linoleic acid, linolenic acid and erucic acid.
Beispiele für ethylenisch ungesättigte C4-C2o_Dicarbon- säureanhydride, die als Monomerkomponente in den Copoly- meren aus ethylenisch ungesättigten C4-C2o-Dicarbonsäure- anhydriden und Vinylaromaten und/oder C2-C36-α-01efinen, die in der Additivmischung der Mineralölrezepturen als Additivkomponente c) partiell und/oder vollständig imidi- siert vorliegen, sind Allylsuccinsäureanhydrid, Bicyclo- heptendicarbonsäureanhydrid, Bicyclooctendicarbonsäurean- hydrid, Carbomethoxymaleinsäureanhydrid, Citraconsäure- anhydrid, Cyclohexendicarbonsäureanhydrid, Dodecencyl- bernsteinsäureanhydrid, Glutaconsäureanhydrid, Itaconsäu- reanhydrid, Maleinsäureanhydrid, Mesaconsäureanhydrid, Methylbicycloheptendicarbonsäureanhydrid und/oder Methyl- cyclohexendicarbonsäureanhydrid, bevorzugt werden Maleinsäureanhydrid und/oder Itakonsäureanhydrid.Examples of ethylenically unsaturated C 4 -C 2 o _ dicarboxylic acid anhydrides, as the monomeric component of the copoly mers of ethylenically unsaturated C 4 -C 2 o-dicarboxylic acid and anhydrides 01efinen -α-vinyl aromatics and / or C 2 -C 36 Partially and / or completely imidized in the additive mixture of the mineral oil formulations as additive component c) are allylsuccinic anhydride, bicyclo-heptenedicarboxylic anhydride, bicyclooctenedicarboxylic anhydride, carbomethoxymaleinic anhydride, dicarbonic acid anhydride, diconic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, cyclic acid anhydride, Maleic anhydride, mesaconic anhydride, methylbicycloheptenedicarboxylic anhydride and / or methylcyclohexenedicarboxylic anhydride, maleic anhydride and / or itaconic anhydride are preferred.
Beispiele für geeignete Vinylaromaten als Comonomere, die als Monomerkomponenten in den partiell und/oder vollständig imidisierten Copolymeren aus ethylenisch ungesättigten C4-C2o_Dicarbonsäureanhydriden c) der Additivmi- schungen enthalten sein können, sind Styrol, α-Methyl- styrol und Vinylpyridin. Beispiele für geeignete C2-C36- -01efine als Comonomere, die als Monomerkomponenten in den partiell und/oder vollständig imidisierten Copolymeren aus ethylenisch ungesättigten C4-C20-Dicarbonsäureanhydriden c) der Additivmi- schungen enthalten sein können, sind ethylenisch ungesättigten Monomere vom Typ C2-C2o-Olefine, C4-C2ι- Acrylsäureester, C5-C22-Methacrylsäureester, C5-Cι4-Vinyl- silane, C6-Cι5-Acrylatsilane, Acrylsäure, Methacrylsäure, Acrylnitril, Vinyloxazolin, Isopropenyloxazolin, Vinyl- pyrrolidon, Amino-Cι-C8-alkyl- (meth) acrylate, C3-C2o- Vinylester, C3-C2o-Vinylether und/oder Hydroxy-Ci-Cs- alkyl- (meth) acrylate .Examples of suitable vinyl aromatic compounds as comonomers, as monomer components in the partially and / or fully imidized copolymers of ethylenically unsaturated C 4 _ -C2o dicarboxylic anhydrides c) the Additivmi- mixtures can be included are styrene, α-methyl styrene and vinyl pyridine. Examples of suitable C 2 -C 36 - -01efins as comonomers which may be present as monomer components in the partially and / or completely imidized copolymers of ethylenically unsaturated C 4 -C 20 dicarboxylic anhydrides c) of the additive mixtures are ethylenically unsaturated monomers of the type C 2 -C 2 o-olefins, C 4 -C 2 ι- acrylic acid esters, C 5 -C 22 methacrylic acid esters, C 5 -Cι 4 -vinyl silanes, C 6 -C 5 -acrylatesilanes, acrylic acid, methacrylic acid, Acrylonitrile, vinyl oxazoline, isopropenyloxazoline, vinyl pyrrolidone, amino-C 8 -C 8 -alkyl- (meth) acrylates, C 3 -C 2 o-vinyl esters, C 3 -C 2 o-vinyl ethers and / or hydroxy-Ci-Cs- alkyl (meth) acrylates.
Bevorzugte Comonomere als Monomerkomponenten in den par- tiell und/oder vollständig imidisierten Copolymeren aus ethylenisch ungesättigten C4-C2o-Dicarbonsäureanhydriden c) der Additivmischungen sind Isobutylen, Diisobutylen, Vinylacetat, Styrol und α-Methylstyrol .Preferred comonomers as monomer components in the partially and / or completely imidized copolymers of ethylenically unsaturated C 4 -C 2 o-dicarboxylic acid anhydrides c) of the additive mixtures are isobutylene, diisobutylene, vinyl acetate, styrene and α-methylstyrene.
Die partiell imidisierten Copolymere aus C4-C2o- ethylenisch ungesättigten Säureanhydriden und Vinylaromaten und/oder C2-C36- -01efinen als Additivkomponente c) haben bevorzugt ein Molverhältnis von 1 : 1 bis 1 : 9 und Molmassen-Gewichtsmittel von 5000 bis 500000, bei denen die partielle Imidisierung mit Ammoniak, C1-C24- Monoalkylaminen, C5-Ci8-aromatischen Monoaminen, C2-Ci8- Monoa inoalkoholen, monoaminierten Poly (C2-C4-alkylen) - oxiden einer Molmasse von 400 bis 3000, und/oder monove- retherten Poly (C2-C4-alkylen) oxiden einer Molmasse von 100 bis 10000 erfolgt ist, wobei das Molverhältnis Anhydridgruppen Copolymer / Ammoniak, Aminogruppen C1-C24- Monoalkylamine, Cg-Cis-aromatische Monoamine, C2-C113- Monoaminoalkohole bzw. monoaminiertes Poly- (C2-C4-alky- len) oxid und/oder Hydroxygruppen Poly- (C2-C4-alkylen) oxid 1 : 1 bis 20 : 1 beträgt.The partially imidized copolymers of C 4 -C 2 o-ethylenically unsaturated acid anhydrides and vinyl aromatics and / or C 2 -C 36 - 01efins as additive component c) preferably have a molar ratio of 1: 1 to 1: 9 and molar mass weight average of 5000 to 500,000, in which the partial imidization with ammonia, C 1 -C 24 monoalkylamines, C 5 -Ci 8 aromatic monoamines, C 2 -Ci 8 monoalcohols, monoaminated poly (C 2 -C 4 alkylene) oxides a molecular weight of 400 to 3000, and / or mono-retarded poly (C 2 -C 4 alkylene) oxides of a molecular weight of 100 to 10000, the molar ratio of anhydride groups copolymer / ammonia, amino groups C 1 -C 24 monoalkylamines, Cg-Cis-aromatic monoamines, C 2 -C 1 1 3 - monoamino alcohols or monoaminated poly- (C 2 -C 4 -alky- len) oxide and / or hydroxyl groups poly (C 2 -C 4 alkylene) oxide is 1: 1 to 20: 1.
Insbesondere geeignet als partiell imidisierte Copolymere aus ethylenisch ungesättigten C4-Co-Dicarbonsäurean- hydriden c) sind mit Ci2-C24-Monoalkyl-aminen wie Oleyla- min, Dodecylamin, Hexadecylamin, Octadecylamin oder Eico- syla in, monosubstituierten Diaminen vom Typ N-Dodecyl- 1, 3-diaminopropan, N-Octadecyl-1, 3-diaminopropan oder N- Octadecylpropylentriamin oder A inoalkoholen wie Aminode- can-10-ol oder Aminohexadecan-16-ol imidisierte Malein- säureanhydrid-Copolymere .Particularly suitable as partially imidized copolymers of ethylenically unsaturated C 4 -co-dicarboxylic acid anhydrides c) are with C 1 -C 24 -monoalkylamines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine or eico-sylain, monosubstituted diamines of the type N-dodecyl-1,3-diaminopropane, N-octadecyl-1,3-diaminopropane or N-octadecylpropylenetriamine or amino alcohols such as aminodecan-10-ol or aminohexadecan-16-ol imidized maleic anhydride copolymers.
Die partiell imidisierten Copolymere aus ungesättigten Dicarbonsäureanhydriden und Vinylaromaten und/oder C2-C36- α-Olefinen als Additivkomponente c) sind besonders bevorzugt partiell mit Ce-C24-Monoalkylaminen imidisierte Ma- leinsäureanhydrid-α-Methylstyrol-Copolymere, bei denen das Molverhältnis Anhydridgruppen im Copolymer / gebunde- nes C6-C24-Monoalkylamin im Copolymer 8 : 1 bis 1,3 : 1 beträgt .The partially imidized copolymers of unsaturated dicarboxylic anhydrides and vinyl aromatics and / or C 2 -C 3 6-α-olefins as additive component c) are particularly preferably maleic anhydride-α-methylstyrene copolymers partially imidized with Ce-C 24 monoalkylamines, in which the molar ratio of anhydride groups in the copolymer / bound C 6 -C 24 -monoalkylamine in the copolymer is 8: 1 to 1.3: 1.
Beispiele für Mineralöle, die die Hauptkomponente in den Rezepturen aus Mineralöl und geringen Anteilen einer Ad- ditivmischung bilden, sind Rohöle und Erdöldestillate mit einem Siedebereich von 100 bis 500°C wie Schmieröle, Ke- rosin, Diesel, Heizöl, schwere Heizöle, Petroleum, Traktorentreibstoff und Crackbenzin. Die Mineralöle können ebenfalls bis 30 Masse% Synthesekohlenwasserstoffe aus der Fischer-Tropsch-Synthese, bis 20 Masse% modifizierte Pflanzenöle auf Basis von Sonnenblumenöl, Sojaöl, Rapsöl, oder Ölen tierischen Ursprungs, Biodiesel und/oder bis 10 Masse% Alkohole wie Methanol oder Ethanol enthalten. Bevorzugt sind die Mineralöle in den Rezepturen aus Mineralöl und geringen Anteilen einer Additivmischung Rohöle oder Brennstofföle aus einem Mitteldestillat mit einem Schwefelgehalt unter 0,05 Masse%, insbesondere Heizöle, Gasöle oder Dieselöle.Examples of mineral oils, which form the main component in the recipes from mineral oil and small proportions of an additive mixture, are crude oils and petroleum distillates with a boiling range from 100 to 500 ° C such as lubricating oils, kerosene, diesel, heating oil, heavy heating oils, petroleum, Tractor fuel and cracked gasoline. The mineral oils can also contain up to 30 mass% synthetic hydrocarbons from the Fischer-Tropsch synthesis, up to 20 mass% modified vegetable oils based on sunflower oil, soybean oil, rapeseed oil, or oils of animal origin, biodiesel and / or up to 10 mass% alcohols such as methanol or ethanol contain. The mineral oils in the formulations of mineral oil and small proportions of an additive mixture are preferred crude oils or fuel oils from a middle distillate with a sulfur content below 0.05% by mass, in particular heating oils, gas oils or diesel oils.
Der bevorzugte Gehalt der Additivmischung im Mineralöl liegt bei 0,01 bis 0,3 Masse%.The preferred content of the additive mixture in the mineral oil is 0.01 to 0.3% by mass.
Das Mineralöl kann weiterhin insgesamt 0 bis 200 Masse%, bezogen auf die Summe der Additivkomponenten a) und b) oder a) und c) oder a) , b) und c) , weitere Additivkomponenten vom Typ Fettsäuregemische, polare Stickstoff er- bindungen, bevorzugt Polyamine, Etheramine, Aminoalkoho- le, Aminsalze, Amide oder Imide von mehrwertigen Carbonsäuren; C7-C3o-Alkohole, Polyalkylenglycole, Ester oder Ether von Polyoxyalkylenverbindungen, nichtmodifizierte Ethylen-Vinylester-Copolymere, Kohlenwasserstoffpolymere, Alkylphenol-Aldehyd-Copolymere, aromatische Verbindungen mit Cs-Cioo-Alkylsubsti-tuenten, carboxylierte Polyamine, Detergentien, Korrosionsinhibitoren, Demulgatoren, Me- talldesaktivatoren, Cetanverbesserer, Entschäumer und/- oder Cosolventien enthalten.The mineral oil can also contain a total of 0 to 200% by mass, based on the sum of additive components a) and b) or a) and c) or a), b) and c), of further additive components of the fatty acid mixture type, polar nitrogen compounds, preferably polyamines, ether amines, amino alcohols, amine salts, amides or imides of polyvalent carboxylic acids; C 7 -C 3 o-alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, unmodified ethylene-vinyl ester copolymers, hydrocarbon polymers, alkylphenol-aldehyde copolymers, aromatic compounds with Cs-Cioo-alkyl substituents, carboxylated polyamines, detergents, corrosion inhibitors, Contain demulsifiers, metal deactivators, cetane improvers, defoamers and / or cosolvents.
Beispiele für die im Mineralöl als weitere Additivkomponenten enthaltenen Fettsäuregemische sind Mischungen aus gesättigten und/oder ungesättigten C6-C40-Carbonsäuren wie Laurinsäure, Palmitinsäure, Ölsäure, Linolensäure, Di er- fettsäuren und Alkenylbernsteinsäuren.Examples of the fatty acid mixtures contained in the mineral oil as further additive components are mixtures of saturated and / or unsaturated C 6 -C 40 carboxylic acids such as lauric acid, palmitic acid, oleic acid, linolenic acid, di-fatty acids and alkenyl succinic acids.
Beispiele für die im Mineralöl als weitere Additivkomponenten enthaltenen polaren Stickstoffverbindungen vom Typ Polyamine sind N-Hexadecyl-1, 3-diaminopropan, N-Octade- cyldipropylentriamin, N-Dodecyl-1, 3-diaminopropan, N,N'- Didodecyl-1, 3-diaminopropan und N,N' -Dioctadecyldipropy- lentriamin.Examples of the polar nitrogen compounds of the type contained in the mineral oil as further additive components Polyamines are N-hexadecyl-1, 3-diaminopropane, N-octadecyldipropylenetriamine, N-dodecyl-1, 3-diaminopropane, N, N'-didodecyl-1, 3-diaminopropane and N, N '-dioctadecyldipropylenentriamine.
Beispiele für die im Mineralöl als weitere Additivkomponenten enthaltenen polaren Stickstoffverbindungen vom Typ Etheramine sind 3-Methoxypropylamin, 3-N-Octyloxypropyl- 1, 3-diaminopropan und 3-N- (2 , 4, 6-trimethyldecyloxypro- pyl) -1, 3-diaminopropan.Examples of the polar nitrogen compounds of the etheramine type contained in the mineral oil as further additive components are 3-methoxypropylamine, 3-N-octyloxypropyl-1, 3-diaminopropane and 3-N- (2, 4, 6-trimethyldecyloxypropyl) -1, 3 -diaminopropan.
Beispiele für die im Mineralöl als weitere Additivkomponenten enthaltenen polaren Stickstoffverbindungen vom Typ Aminoalkohole sind Aminopentan-5-ol, Aminoundecan-11-ol und 2-Amino-2-methylpropanol .Examples of the polar nitrogen compounds of the amino alcohol type contained in the mineral oil as further additive components are aminopentan-5-ol, aminoundecan-11-ol and 2-amino-2-methylpropanol.
Beispiele für die den polaren Stickstoffverbindungen vom Typ Aminsalze, Amide oder Imide von mehrwertigen Carbonsäuren als weitere Additivkomponenten zugrunde liegenden Amine sind C8-C4o-Amine wie hydriertes Tallamin, Tetra- decylamin, Eicosylamin, Dioctadecylamin, Methylbehenyla- min, N-Oleyl-1, 3-diaminopropan, N-Stearyl-l-methyl-1, 3- diaminopropan oder N-Oleyldipropylentriamin.Examples of the amines on which the polar nitrogen compounds of the type amine salts, amides or imides of polyvalent carboxylic acids are based as further additive components are C 8 -C 4 o-amines such as hydrogenated tallamine, tetra-decylamine, eicosylamine, dioctadecylamine, methylbehenylamine, N-oleyl -1, 3-diaminopropane, N-stearyl-l-methyl-1,3-diaminopropane or N-oleyldipropylenetriamine.
Beispiele für die den polaren Stickstoffverbindungen vom Typ Aminsalze oder Amide von mehrwertigen Carbonsäuren als weitere Additivkomponenten zugrunde liegenden mehrwertigen Carbonsäuren sind Phthalsäure, Isophthalsäure, Terephthalsäure, Naphthalindicarbonsäure, Ethylendiamin- tetraessigsäure und Cyclohexandicarbonsäure.Examples of the polyvalent carboxylic acids on which the polar nitrogen compounds of the type amine salts or amides of polyvalent carboxylic acids are based as further additive components are phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, ethylenediaminetetraacetic acid and cyclohexanedicarboxylic acid.
Spezielle Beispiele für die im Mineralöl als weitere Additivkomponenten enthaltenen polaren Stickstoffverbindun- gen vom Typ Aminsalze sind N-Methyl-triethanolammoniumdi- stearylesterchlorid und N-Methyltriethanolammoniumdi- stearylestermethosulfat .Specific examples of the polar nitrogen compounds contained in mineral oil as additional additive components Amine salts are N-methyl-triethanolammonium disearyl ester chloride and N-methyltriethanolammonium disearyl ester methosulfate.
Beispiele für C7-C30-Alkohole, die als weitere Additivkomponenten im Mineralöl enthalten sein können, sind Dodeca- nol, Stearylalkohol und Cerylalkohol .Examples of C 7 -C 30 alcohols which may be contained in the mineral oil as further additive components are dodecanol, stearyl alcohol and ceryl alcohol.
Beispiele für Polyalkylenglycole, die als weitere Addi- tivkomponenten im Mineralöl enthalten sein können, sind Polyethylenglycole, Polypropylenglycole und Ethylenoxid- Propylenoxid-Copolymere mit Molmassen von 500 bis 5000.Examples of polyalkylene glycols which may be present in the mineral oil as further additive components are polyethylene glycols, polypropylene glycols and ethylene oxide / propylene oxide copolymers with molecular weights from 500 to 5000.
Beispiele für Ester von Polyoxyalkylenverbindungen, die als weitere Additivkomponenten im Mineralöl enthalten sein können, sind Cι0-C24-Monoalkylester- oder Dialky- lester von Polyalkylenglycolen wie Polyethylenglycolmo- nostearylester oder Polypropylenglycoldioleat .Examples of esters of polyoxyalkylene compounds which may be contained in the mineral oil as further additive components are C 0 -C 24 -monoalkyl esters or dialkyl esters of polyalkylene glycols such as polyethylene glycol monostearyl ester or polypropylene glycol dioleate.
Beispiele für Ether von Polyoxyalkylenverbindungen, die als weitere Additivkomponenten im Mineralöl enthalten sein können, sind Cι-C4-Monoalkylether oder Dialkylether von Polyalkylenglycolen wie Polyethylenglycolmonomethy- lether oder Polypropylenglycoldibutylether .Examples of ethers of polyoxyalkylene compounds which may be present in the mineral oil as further additive components are C 1 -C 4 -monoalkyl ethers or dialkyl ethers of polyalkylene glycols such as polyethylene glycol monomethyl ether or polypropylene glycol dibutyl ether.
Beispiele für Kohlenwasserstoffpolymere, die als weitere Additivkomponenten im Mineralöl enthalten sein können, sind Copolymere aus Ethylen und C3-C20- -Olefinen wie E- thylen-Propylen-Copolymere oder Ethylen-Dodecen-Copolyme- re oder hydrierte Polymere von mehrfach ungesättigten Monomeren vom Typ hydrierte Dien-Copolymere wie hydriertes Polybutadien oder hydriertes Polyisopren mit Molmassen- Zahlenmitteln bis 30000. Beispiele für Alkylphenol-Aldehyd-Copolymere, die als weitere Additivkomponenten im Mineralöl enthalten sein können, sind Copolymere, die durch Umsetzung alkylierter Phenole wie Phenol-Propylenoligomer-Addukten mit Parafor- maldehyd hergestellt werden können.Examples of hydrocarbon polymers which may be contained in the mineral oil as further additive components are copolymers of ethylene and C 3 -C 20 - olefins such as ethylene-propylene copolymers or ethylene-dodecene copolymers or hydrogenated polymers of polyunsaturated monomers of the type hydrogenated diene copolymers such as hydrogenated polybutadiene or hydrogenated polyisoprene with number average molecular weights up to 30,000. Examples of alkylphenol-aldehyde copolymers which may be present in the mineral oil as further additive components are copolymers which can be prepared by reacting alkylated phenols such as phenol-propylene oligomer adducts with paraformaldehyde.
Beispiele für aromatische Verbindungen mit C8-Cι0o- Alkylsubstituenten, die als weitere Additivkomponenten im Mineralöl enthalten sein können, sind Verbindungen, die durch Friedel-Krafts-Kondensation halogenierter Kohlenwasserstoffe wie halogeniertem Polyethylenwachs mit aromatischen Kohlenwasserstoffen wie Benzen oder Naphthalin hergestellt werden können.Examples of aromatic compounds having C 8 -Cι 0 o- alkyl substituents which may be contained as other additive components in mineral oil, are compounds which are halogenated by Friedel-Crafts condensation hydrocarbons such as halogenated polyethylene wax with aromatic hydrocarbons such as benzene or naphthalene may be prepared.
Beispiele für Detergentien, die als weitere Additivkomponenten im Mineralöl enthalten sein können, sind aliphati- sche Sulfonsäuren wie Cs-C3o-Alkansulfonate oder aroma- tisch-aliphatische Alkansulfonate, insbesondere Nonylben- zolsulfonsäure, Dodecylbenzolsulfonsäure, Didodecylben- zolsulfonsäure und Nonylnaphthalinsulfonsäure .Examples of detergents which may be present in the mineral oil as further additive components are aliphatic sulfonic acids such as Cs-C 3 o-alkanesulfonates or aromatic-aliphatic alkanesulfonates, in particular nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid and nonylnaphthalenesulfonic acid.
Beispiele für Demulgatoren, die als weitere Additivkomponenten im Mineralöl enthalten sein können, sind oxalky- lierte Phenol-Formaldehyd-Kondensate, Polyalkylenglycol- modifizierte Diglycidether, Polyesteramine oder alkoxy- lierte Fettsäuren.Examples of demulsifiers which may be present in the mineral oil as further additive components are oxyalkylated phenol-formaldehyde condensates, polyalkylene glycol-modified diglycidyl ethers, polyesteramines or alkoxylated fatty acids.
Beispiele für Cetanverbesserer, die als weitere Additiv- komponenten im Mineralöl enthalten sein können, sind organische Salpetersäureester wie Ethylhexylnitrat, Cyclo- hexylnitrat oder Ethoxyethylnitrat, oder lösliche organische Peroxide, Hydroperoxide oder Perester. Bevorzugte Entschäumer, die als weitere Additivkomponenten im Mineralöl enthalten sein können, sind Polyalkyle- noxid-Siloxan-Blockcopolymere und carboxylierte Polyami- ne .Examples of cetane improvers which may be present in the mineral oil as further additive components are organic nitric acid esters such as ethylhexyl nitrate, cyclohexyl nitrate or ethoxyethyl nitrate, or soluble organic peroxides, hydroperoxides or peresters. Preferred defoamers, which may be contained in the mineral oil as further additive components, are polyalkylene oxide-siloxane block copolymers and carboxylated polyamines.
Beispiele für Polyalkylenoxid-Siloxan-Blockcopolymere sind Blockcopolymere, die eine Kombination trifunktionel- ler Siloxanblöcke wie Monomethylsiloxangruppen, difunkti- oneller Siloxangruppen wie Dimethylsiloxangruppen und monofunktioneiler Siloxangruppen wie Trimethylsiloxangruppen enthalten, eine bevorzugte Länge der Siloxanblöcke beträgt 5 bis 20 Monomereinheiten. Für die Polyalkylen- oxid-Blöcke beträgt die bevorzugte Länge 2 bis 40 Mono- mereinheiten, bevorzugt werden Polyoxyalkylenblöcke aus Ethylenoxid- und/oder Propylenoxid-Einheiten.Examples of polyalkylene oxide-siloxane block copolymers are block copolymers which contain a combination of trifunctional siloxane blocks such as monomethylsiloxane groups, difunctional siloxane groups such as dimethylsiloxane groups and monofunctional siloxane groups such as trimethylsiloxane groups, a preferred length of the siloxane units being 5 bis 20 siloxane blocks. For the polyalkylene oxide blocks, the preferred length is 2 to 40 monomer units; polyoxyalkylene blocks composed of ethylene oxide and / or propylene oxide units are preferred.
Beispiele für carboxylierte Polyamine als Entschäumer sind Reaktionsprodukte aus C8-C24-Fettsäuren und Aminen wie Ethylendiamin, Butylendiamin, Diethylentriamin und Pentaethylenhexamin-1 , 2-diaminobutanol .Examples of carboxylated polyamines as defoamers are reaction products of C 8 -C 24 fatty acids and amines such as ethylenediamine, butylenediamine, diethylenetriamine and pentaethylenehexamine-1,2-diaminobutanol.
Beispiele für Cosolventien, die als weitere Additivkomponenten in den Zusammensetzungen aus Mineralöl enthalten sein können, sind Benzinfraktionen, Toluen, Xylen, Ethyl- benzen, Isononanol, Ethylhexanol, Dodecylphenol, epoxi- diertes Rapsöl und epoxidiertes Sojabohnenöl .Examples of cosolvents which can be contained in the mineral oil compositions as further additive components are gasoline fractions, toluene, xylene, ethylbenzene, isononanol, ethylhexanol, dodecylphenol, epoxidized rapeseed oil and epoxidized soybean oil.
Die Rezepturen aus Mineralöl als Hauptkomponente und ge- ringen Anteilen einer Additivmischung werden nach einem Verfahren hergestellt, bei dem erfindungsgemäß Rezepturen, die die Additivkomponenten a) durch polare Gruppen modifizierte Ethylen-Vinylester- Copolymere mit Molmassengewichtsmitteln von 3000 bis 50000 und einem Ethylenanteil von 50 bis 90 Masse%, und b) C2-C6-oxyalkylverbrückte Cι2-C40-Monocarbonsäuren, und/oder c) partiell und/oder vollständig imidisierte Copolymere aus C4-C2o-ungesättigten Dicarbonsäureanhydriden und Vinylaromaten und/oder C2-C35-α-01efinen enthalten, wobei der Gehalt der Additivmischung im Mineralöl 0,005 bis 1 Masse% und das Masseverhältnis der Additivkomponenten a/b oder a/c oder a/ (b+c) 10 : 90 bis 90 : 10 beträgt, nach einem Vorhomogenisierungsverfahren hergestellt werden, bei dem in der ersten Verfahrensstufe 1 bis 60 Masse% Addi- tivkomponenten enthaltende Lösungen in Mineralöl- Mitteldestillaten bei 20 bis 90°C hergestellt werden, und in der zweiten Verfahrensstufe die Additivkomponenten enthaltenden Lösungen mit dem Mineralöl als Hauptkomponente homogenisiert werden, wobei dem Mineralöl insgesamt 0 bis 200 Masse%, bezogen auf die Summe der Additivkomponenten a) und b) oder a) und c) oder a) , b) und c) , weitere Additivkomponenten in der ersten und/oder zweiten Verfahrensstufe zugesetzt werden.The formulations made from mineral oil as the main component and low proportions of an additive mixture are produced by a process in which, according to the invention, formulations containing the additive components a) ethylene-vinyl ester copolymers modified by polar groups with molecular weights of 3000 to 50,000 and an ethylene content of 50 to 90% by mass, and b) C 2 -C 6 -oxyalkyl-bridged C 2 -C 40 monocarboxylic acids, and / or c) contain partially and / or completely imidized copolymers of C 4 -C 2 o-unsaturated dicarboxylic acid anhydrides and vinyl aromatics and / or C 2 -C 35 -α-01efins, the content of the additive mixture in the mineral oil being 0.005 to 1% by mass and the mass ratio of the additive components a / b or a / c or a / (b + c) 10: 90 to 90: 10, are prepared by a pre-homogenization process in which, in the first process step, solutions in mineral oil middle distillates containing additive components containing 1 to 60% by mass are produced at 20 to 90 ° C, and in the second process stage, the solutions containing additive components are homogenized with the mineral oil as the main component, the mineral oil being 0 to 200 Ma %, based on the sum of the additive components a) and b) or a) and c) or a), b) and c), further additive components are added in the first and / or second process stage.
Die erfindungsgemäßen Rezepturen aus Mineralöl als Hauptkomponente und geringen Anteilen einer Additivmischung sind bevorzugt als bei niedrigen Temperaturen zu trans- portierende fließfähige Medien und als Mineralölkraftstoff hoher Schmierwirkung und Fliessfähigkeit geeignet.The formulations of mineral oil as the main component and small proportions of an additive mixture according to the invention are preferred as being too low at low portable flowable media and suitable as mineral oil fuel with high lubrication and flowability.
Beispiele für die bei niedrigen Temperaturen zu transpor- tierenden fließfähigen Medien sind der Transport von Rohöl-Rezepturen von der Förderstelle des Rohöls durch Pipelines zur Verladung und zur Lagerung sowie der Transport von Diesel- oder Heizölrezepturen in Rohrleitungen.Examples of the flowable media to be transported at low temperatures are the transportation of crude oil formulations from the crude oil production site through pipelines for loading and storage, and the transportation of diesel or heating oil formulations in pipelines.
Die Erfindung wird durch nachfolgende Beispiele erläutert. The invention is illustrated by the following examples.
BEISPIELEEXAMPLES
Die Kennzahlen wurden nach folgenden Prüfverfahren ermit- telt :The key figures were determined using the following test methods:
Cloud Point (CP) : DIN EN 23 015 Cold Filter Plugging Point (CFPP) : EN 116 Siedeanalyse : EN ISO 3405, ASTM D 86 IBP : Initial Boiling Point FBP : Final Boiling PointCloud Point (CP): DIN EN 23 015 Cold Filter Plugging Point (CFPP): EN 116 Boiling Analysis: EN ISO 3405, ASTM D 86 IBP: Initial Boiling Point FBP: Final Boiling Point
Vinylacetatgehalt : modifiziertes Verfahren nach ISO 8995, DIN 16778 Teil 2 : 2 g Probe werden auf 0,001 g genau eingewogen und in einem 300 ml Erlenmeyerkolben mit 70 ml destilliertem Xylen und 2 Siedeperlen rd. 15 min unter Erwärmung am Rückflusskühler gelöst. Anschließend werden rd. 30 ml Ethanol langsam durch den Rückflusskühler zugegeben, der Erlen- meyerkolben wird von der Heizplatte genommen, es werden 30 ml Ethanol, 0,5 n KOH aus der Bürette und 2 Siedeperlen hinzugefügt, und die Probe wird 1 h am Rückfluss gekocht. Danach wird die Probe erneut vom Rückfluss genommen, mit 30 ml methanolisch-wässriger 0,5 n HCl und 2 Siedeperlen versetzt und 15 min am Rückfluss weitergekocht. Die Probe wird anschließend nach Zugabe von 2 bis 3 Tropfen Phenolphthalein-Lösung (1 Masse% in Ethanol) mit ethanolischer 0,5 n KOH tropfenweise unter Schütteln bis zum Farbumschlag nach rot titriert. Parallel dazu ist ein Blindwert zu ermitteln. ( V - BW ) x F x 43Vinyl acetate content: modified method according to ISO 8995, DIN 16778 part 2: 2 g sample are weighed to the nearest 0.001 g and in a 300 ml Erlenmeyer flask with 70 ml distilled xylene and 2 boiling pearls approx. Solved for 15 min while heating the reflux condenser. Then approx. 30 ml of ethanol are slowly added through the reflux condenser, the Erlenmeyer flask is removed from the hotplate, 30 ml of ethanol, 0.5 N KOH from the burette and 2 boiling pearls are added, and the sample is refluxed for 1 h. The sample is then taken again from the reflux, 30 ml of methanolic aqueous 0.5 N HCl and 2 boiling pearls are added and the mixture is boiled under reflux for 15 min. After adding 2 to 3 drops of phenolphthalein solution (1 mass% in ethanol), the sample is then titrated dropwise with ethanolic 0.5 N KOH while shaking until the color changes to red. A blank value must be determined in parallel. (V - BW) x F x 43
Vinylacetatgehalt in Masse% = 10 x E E = Einwaage in gMass of vinyl acetate% = 10 x E E = weight in g
F = Faktor der ethanolischen 0,5 n KOHF = factor of the ethanolic 0.5 N KOH
V = Verbrauch in ml an 0,5 n ethanolischer KOH für die Probe B = Verbrauch in ml an 0,5 n ethanolischer KOH für den BlindwertV = consumption in ml of 0.5 N ethanolic KOH for the sample B = consumption in ml of 0.5 N ethanolic KOH for the blank value
Schmierfähigkeit: Lubricity-Test (korrigierter „wear scar diameter" bei 60°C) nach ISO 12156-1Lubricity: Lubricity test (corrected "wear scar diameter" at 60 ° C) according to ISO 12156-1
Kurzzeitsediment-Test :Short-term sediment test:
Zur Überprüfung der Sedimentationsneigung auskristallisierter Paraffine im Mineralöl wird eine 500 ml - Probe 16 h in einem Messzylinder gelagert und anschließend die oben anstehenden 80 Vol% der Probe abgesaugt und verworfen. Die verbliebenen 20 Vol% der Probe (100 ml) werden bei 40°C homogenisiert und davon der Cloud Point (CP) nach DIN EN 23 015 bestimmt.To check the tendency to sedimentation of crystallized paraffins in mineral oil, a 500 ml sample is stored in a measuring cylinder for 16 h and then the 80% by volume of the sample above is sucked off and discarded. The remaining 20 vol% of the sample (100 ml) are homogenized at 40 ° C and the cloud point (CP) is determined according to DIN EN 23 015.
SEDAB Filtrations-Test :SEDAB Filtration Test:
Eine 500 ml-Mineralölprobe wird 20 x vertikal geschüttelt, 16 h bei 10°C temperiert, 10 x vertikal geschüttelt, und die gesamte Probe wird auf einmal durch ein Filter aus Cellulosenitrat (Durchmesser 50 mm, Porengrös- se 0,8μm), die auf einen Saugtopf mit einem Vacuum von rd. 200 hPa aufgesetzt ist, filtriert. Ermittelt wird die Zeit (s) , in der die Probe durch das Filter läuft. Der SEDAB-Filtrationstest gilt als bestanden, wenn die Probe in einem Zeitraum < 120 s das Filter passiert. Beispiel 1A 500 ml mineral oil sample is shaken 20 times vertically, temperature-controlled at 10 ° C. for 16 h, shaken 10 times vertically, and the entire sample is passed through a filter made of cellulose nitrate (diameter 50 mm, pore size 0.8 μm) on a suction cup with a vacuum of approx. 200 hPa is applied, filtered. The time (s) during which the sample runs through the filter is determined. The SEDAB filtration test is passed if the sample passes the filter within a period of <120 s. example 1
1.1 Ausgangsprodukte1.1 Starting products
1.1.1 Unadditivierter Diesel1.1.1 Unadditized Diesel
Charge : 16080601 Test DK 1 Charakterisierung : Cloud Point (CP) : +6 °C ; Cold Filter Plugging Point (CFPP) : +2 °C Lubricity-Test : 563 μ Siedeanalyse :Batch: 16080601 Test DK 1 Characterization: Cloud Point (CP): +6 ° C; Cold Filter Plugging Point (CFPP): +2 ° C Lubricity test: 563 μ boiling analysis:
Destillierte Menge (Vol.-%) / Temperatur (°C)Distilled quantity (vol.%) / Temperature (° C)
IBP 10 20 30 40 50 60 70 80 90 FBPIBP 10 20 30 40 50 60 70 80 90 FBP
189 243 259 271 281 292 303 317 334 357 385189 243 259 271 281 292 303 317 334 357 385
1.1.2 Additivkomponente a) Mischung aus 60 Masse% eines Vinylacetat-gepfropften E- thylen-Vinylacetat-Copolymerwachses (hergestellt nach DD 293 125 A5, Gesamtgehalt an Vinylacetat 45 Massel, Molmassen-Gewichtsmittel 3800 g/mol, Vinylacetatgehalt des nichtgepfropften Ξthylen-Vinylacetat-Copolymerwachses 32 Masse%) und 40 Masse% eines nichtgepfropften Ethylen- Vinylacetat-Copolymerwachses (Hersteller LEUNA Polymer GmbH, Vinylacetatgehalt 32 Masse%, Molmassen-Zahlenmittel 1920 g/mol) .1.1.2 Additive component a) Mixture of 60% by weight of a vinyl acetate-grafted ethylene-vinyl acetate copolymer wax (manufactured according to DD 293 125 A5, total vinyl acetate content 45 pigments, weight average molecular weight 3800 g / mol, vinyl acetate content of the non-grafted ethylene-vinyl acetate Copolymer wax 32 mass%) and 40 mass% of a non-grafted ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32 mass%, molar mass number average 1920 g / mol).
1.1.3 Additivkomponente b)1.1.3 Additive component b)
Gemisch C3-oxyalkylverbrückter ungesättigter Ci8-C24- Carbonsäuren, Veresterungsgrad 92 Mol%, Gehalt an Cι8- ungesättigten Fettsäuren 32 Masse , Gehalt an C22- ungesättigten Fettsäuren 48 Massel, Jodzahl 96Mixture of C 3 -oxyalkyl-bridged unsaturated Ci 8 -C 24 carboxylic acids, degree of esterification 92 mol%, content of C 8 - unsaturated fatty acids 32 mass, content of C 22 - unsaturated fatty acids 48 masses, iodine number 96
1.1.4 Additivkomponente c) Styrol-Maleinsäureanhydrid-Copolymer, mit Ci6-Cι8-Fettamin teilimidisiert, Molmassenzahlenmittel 9500 g/mol, Säurezahl 291.1.4 Additive component c) styrene-maleic anhydride copolymer, partially imidized with Ci 6 -C 8 -fatty amine, average molecular weight 9500 g / mol, acid number 29
1.1.5 Weitere Additivkomponenten: Didodecylamidoben- zoat1.1.5 Other additive components: Didodecylamidoben- zoat
1.2 Herstellung der Additivkomponenten enthaltenden Lösungen in Mineralöl-Mitteldestillaten1.2 Preparation of the solutions containing additive components in mineral oil middle distillates
In einem Rührbehälter werden 25 kg einer 4Öligen Lösung der Additivkomponente c) in C8-C9-Dieselaromatenfraktion, 50 kg einer 5Öligen Lösung der Additivkomponente a) in einem aromatischen Kohlenwasserstoffgemisch (Solvesso) , 25 kg der Additivkomponente b) und 1 kg der weiteren Ad- ditivkomponenten Didodecylamidobenzoat 90 min bei 65°C gemischt und die Mischung in einen Vorratstank überführt .25 kg of a 4-oil solution of additive component c) in a C 8 -C 9 diesel aromatic fraction, 50 kg of a 5-oil solution of additive component a) in an aromatic hydrocarbon mixture (Solvesso), 25 kg of additive component b) and 1 kg of the other are placed in a stirred container Additive components didodecylamidobenzoate mixed at 65 ° C for 90 min and the mixture transferred to a storage tank.
1.3 Herstellung der Rezeptur aus Mineralöl1.3 Production of the recipe from mineral oil
In einen Produktstrom nichtadditiviertem Diesel Charge 16080601 bei 800 kg/min wird mit 0,48 kg/min die Additivlösung nach 1.2 eingespritzt und in einen Lagertank überführt .The additive solution according to 1.2 is injected into a product stream of non-additized diesel batch 16080601 at 800 kg / min at 0.48 kg / min and transferred to a storage tank.
Die Ausprüfung der Kältebeständigkeit der Mineralölrezeptur ergibt einen CFPP-Wert von -10°C. Der Lubricity-Test ergibt einen „wear scar diameter" von 395 μm. Wird unter gleichen Bedingungen eine Mineralölrezeptur hergestellt, die ausschließlich das nichtgepfropfte Copo- lymerwachs als Additiv enthält, so beträgt der CFPP-Wert -3°C und der „wear scar diameter" von 520 μm.Testing the cold resistance of the mineral oil formulation gives a CFPP value of -10 ° C. The lubricity test shows a "wear scar diameter" of 395 μm. If a mineral oil formulation is produced under the same conditions and contains only the non-grafted copolymer wax as an additive, the CFPP value is -3 ° C and the "wear scar diameter" is 520 μm.
Beispiel 2Example 2
2.1 Ausgangsprodukte2.1 Starting products
2.1.1 Unadditivierter Diesel2.1.1 Unadditized Diesel
Charge : 030210 DGO Test DK 2Batch: 030210 DGO Test DK 2
Charakterisierung : Cloud Point (CP) : +8 °C ;Characterization: Cloud Point (CP): +8 ° C;
Cold Filter Plugging Point (CFPP) : +3 °C Siedeanalyse :Cold Filter Plugging Point (CFPP): +3 ° C Boiling analysis:
Destillierte Menge (Vol.-!) / Temperatur (°C)Distilled quantity (Vol.-!) / Temperature (° C)
IBP 10 20 30 40 50 60 70 80 90 FBPIBP 10 20 30 40 50 60 70 80 90 FBP
235 266 279 291 301 310 320 337 342 357 374235 266 279 291 301 310 320 337 342 357 374
Lubricity-Test : 556 μmLubricity test: 556 μm
2.1.2 Additivkomponente a)2.1.2 Additive component a)
Mischung aus 50 Massel eines teilverseiften Ethylen- Vinylacetat-Copolymerwachses (Molmassen-Gewichtsmittel 1600 g/mol, Vinylacetatgehalt des nichtverseiften Ethylen-Vinylacetat-Copolymerwachses 29 Massel, Versei- fungsgrad 15 Mol!) und 50 Masse! eines nichtverseiften Ethylen-Vinylacetat-Copolymerwachses (Hersteller LEUNA Polymer GmbH, Vinylacetatgehalt 29 Massel, Molmassen- Zahlenmittel 2015 g/mol.Mixture of 50 pounds of partially saponified ethylene-vinyl acetate copolymer wax (weight average molecular weight 1600 g / mol, vinyl acetate content of the unsaponified ethylene-vinyl acetate copolymer wax 29 pounds, degree of saponification 15 moles!) And 50 masses! a non-saponified ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 29 brass, number average molecular weight 2015 g / mol.
2.1.3 Additivkomponente b) : Triester von Pentae- rythrit mit Stearinsäure2.1.3 Additive component b): Triester of pentaerythritol with stearic acid
2.1.4 Additivkomponente c)2.1.4 Additive component c)
Styrol -Maleinsäureanhydrid-Copolymer, mit Ci6-Cι8-Fettamin teilimidisiert , Molmassenzahlenmittel 21000 g/mol , Säurezahl 37Styrene-maleic anhydride copolymer, partially imidized with Ci 6 -C 8 fatty amine, average molecular weight 21000 g / mol, acid number 37
2.1.5 Weitere Additivkomponente2.1.5 Other additive components
Vinylacetat-Ethylhexylacrylat-Copolymer (Molverhältnis 1,5 : 1, Molmassen-Zahlenmittel 13500)Vinyl acetate-ethylhexyl acrylate copolymer (molar ratio 1.5: 1, molar mass number average 13500)
2.2 Herstellung der Additivkomponenten enthaltenden Lösungen in Mineralöl-Mitteldestillaten2.2 Production of the solutions containing additive components in mineral oil middle distillates
In einem Rührbehälter werden 25 kg einer 40!igen Lösung der Additivkomponente c) in Cs-Cg-Diesel-Aromatenfrak- tion, 50 kg einer 60!igen Lösung der Additivkomponente a) in Cs-Cg-Diesel-Aromatenfraktion, 25 kg der Additivkomponente b) und 20 kg einer 2Öligen Lösung der weiteren Additivkomponente Vinylacetat-Ethylhexylacrylat-Copolymer in Toluen 90 min bei 65°C gemischt, und die Mischung in einen Vorratstank überführt. 2.3 Herstellung der Rezeptur aus Mineralöl25 kg of a 40% solution of the additive component c) in a Cs-Cg-Diesel aromatic fraction, 50 kg of a 60% solution of the additive component a) in a Cs-Cg-Diesel aromatic fraction, 25 kg of the additive component are placed in a stirred tank b) and 20 kg of a 2-oil solution of the further additive component vinyl acetate-ethylhexyl acrylate copolymer are mixed in toluene at 65 ° C. for 90 min, and the mixture is transferred to a storage tank. 2.3 Production of the recipe from mineral oil
In einen Produktstrom nichtadditiviertem Diesel Charge 030210 bei 800 kg/min wird mit 0,12 kg/min die Additiv- lösung nach 2.2 eingespritzt und in einen Lagertank überführt .The additive solution according to 2.2 is injected into a product stream of non-additized Diesel Charge 030210 at 800 kg / min at 0.12 kg / min and transferred to a storage tank.
Die Ausprüfung der Kältebeständigkeit der Mineralölrezeptur ergibt einen CFPP-Wert von -10°C. Der Lubricity-Test ergibt einen „wear scar diameter" von 387 μm.Testing the cold resistance of the mineral oil formulation gives a CFPP value of -10 ° C. The lubricity test shows a "wear scar diameter" of 387 μm.
Wird unter gleichen Bedingungen eine Mineralölrezeptur hergestellt, die ausschließlich das nichtverseifte Copo- lymerwachs als Additiv enthält, so beträgt der CFPP-Wert -5°C und der „wear scar diameter" 528 μm.If a mineral oil recipe is produced under the same conditions and contains only the unsaponified copolymer wax as an additive, the CFPP value is -5 ° C and the "wear scar diameter" is 528 μm.
Beispiel 3Example 3
3.1 Ausgangsprodukte3.1 Starting products
3.1.1 Unadditiviertes Heizöl3.1.1 Unadditized heating oil
Charge : 030225 Test HEL 1 Charakterisierung : Cloud Point (CP) : +1 °C ; Cold Filter Plugging Point (CFPP) : -1 °CBatch: 030225 Test HEL 1 Characterization: Cloud Point (CP): +1 ° C; Cold filter plugging point (CFPP): -1 ° C
Siedeanalyse :Boiling analysis:
Destillierte Menge (Vol.-!) / Temperatur (°C)Distilled quantity (Vol.-!) / Temperature (° C)
IBP 10 20 30 40 50 60 70 80 90 FBPIBP 10 20 30 40 50 60 70 80 90 FBP
165 196 213 230 249 269 290 310 327 344 363 3.1.2 Additivkomponente a)165 196 213 230 249 269 290 310 327 344 363 3.1.2 Additive component a)
Mischung aus 40 Masse! eines oxidierten Ethylen- Vinylacetat-Copolymerwachses (Molmassen-Zahlenmittel 950 g/mol, Vinylacetatgehalt 29,5 Massel, Säurezahl 18 mg KOH/g, OH-Zahl 70 mg KOH/g) und 60 Masse! eines nichtoxi- dierten Ethylen-Vinylacetat-Copolymerwachses (Hersteller LEUNA Polymer GmbH, Vinylacetatgehalt 32,5 Massel, Molmassen-Gewichtsmittel 4400 g/mol.Mixture of 40 mass! an oxidized ethylene-vinyl acetate copolymer wax (number average molecular weight 950 g / mol, vinyl acetate content 29.5 pounds, acid number 18 mg KOH / g, OH number 70 mg KOH / g) and 60 parts by weight! of an unoxidized ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32.5 pounds, weight average molar mass 4400 g / mol.
3.1.3 Additivkomponente b) : Diester von Propylengly- col mit Ölsäure3.1.3 Additive component b): diester of propylene glycol with oleic acid
3.1.4 Additivkomponente c) :3.1.4 Additive component c):
Styrol-Maleinsäureanhydrid-Copolymer, mit Ci6-Cι8-Fettamin teilimidisiert, Molmassenzahlenmittel 9500 g/mol, Säurezahl 25Styrene-maleic anhydride copolymer, partially imidized with Ci 6 -C 8 fatty amine, average molecular weight 9500 g / mol, acid number 25
3.1.5 Weitere Additivkomponente: 2-Amino-2-methyldo- decanol3.1.5 Further additive component: 2-amino-2-methyldodecanol
3.2 Herstellung der Additivkomponenten enthaltenden Lösungen in Mineralöl-Mitteldestillaten3.2 Preparation of the solutions containing additive components in mineral oil middle distillates
In einem Rührbehälter werden 25 kg einer 4Öligen Lösung der Additivkomponente c) in C8-C9-Diesel-Aromatenfrak- tion, 10,0 kg einer 60!igen Lösung der Additivkomponente a) in Cs-Cg-Diesel-Aromatenfraktion, 10 kg der Additivkomponente b) und 2,0 kg der weiteren Additivkomponente 2-Amino-2-methyl-dodecanol 90 min bei 65°C gemischt, und die Mischung in einen Vorratstank überführt. 3.3 Herstellung der Rezeptur aus Mineralöl25 kg of a 4-oil solution of additive component c) in C 8 -C 9 diesel aromatic fraction, 10.0 kg of a 60% solution of additive component a) in Cs-Cg diesel aromatic fraction, 10 kg are placed in a stirred container the additive component b) and 2.0 kg of the further additive component 2-amino-2-methyl-dodecanol are mixed for 90 min at 65 ° C., and the mixture is transferred to a storage tank. 3.3 Production of the recipe from mineral oil
In einen Produktstrom nichtadditiviertes Heizöl Charge 030225 bei 800 kg/min wird mit 0,24 kg/min die Additiv- lösung nach 3.2 eingespritzt und in einen Lagertank überführt .The additive solution according to 3.2 is injected into a product stream of non-additized heating oil batch 030225 at 800 kg / min at 0.24 kg / min and transferred to a storage tank.
Die Ausprüfung der Kältebeständigkeit der Mineralölrezeptur ergibt einen CFPP-Wert von -15°C.Testing the cold resistance of the mineral oil formulation gives a CFPP value of -15 ° C.
Wird unter gleichen Bedingungen eine Mineralölrezeptur hergestellt, die ausschließlich das nichtoxidierte Copo- lymerwachs als Additiv enthält, so beträgt der CFPP-Wert -13°C.If a mineral oil recipe is produced under the same conditions and contains only the non-oxidized copolymer wax as an additive, the CFPP value is -13 ° C.
Beispiel 4Example 4
4.1 Ausgangsprodukte4.1 Starting products
4.1.1 Unadditiviertes Heizöl : Charge 030218 Test HEL 24.1.1 Unadditized heating oil: batch 030218 test HEL 2
Charakterisierung :Characterization:
Cloud Point (CP) : +2 °C ;Cloud Point (CP): +2 ° C;
Cold Filter Plugging Point (CFPP) : -1 °CCold filter plugging point (CFPP): -1 ° C
Siedeanalyse :Boiling analysis:
Destillierte Menge (Vol.-!) / Temperatur (°C)Distilled quantity (Vol.-!) / Temperature (° C)
IBP 10 20 30 40 50 60 70 80 90 FBPIBP 10 20 30 40 50 60 70 80 90 FBP
173 194 207 225 247 273 299 320 337 355 379 4.1.2 Additivkomponente a)173 194 207 225 247 273 299 320 337 355 379 4.1.2 Additive component a)
Mischung aus 40 Masse! eines Vinylacetatgepfropften E- thylen-Vinylacetat-Copolymerwachses (hergestellt nach DD 293 125 A5, Gesamtgehalt an Vinylacetat 38 Massel, Molmassen-Gewichtsmittel 6400 g/mol, Vinylacetatgehalt des nichtgepfropften Ethylen-Vinylacetat-Copolymerwachses 32 Masse!) und 60 Masse! eines nichtgepfropften Ethylen-Vi- nylacetat-Copolymerwachses (Hersteller LEUNA Polymer GmbH, Vinylacetatgehalt 32 Massel, Molmassen-Gewichtsmittel 4400 g/mol.Mixture of 40 mass! a vinyl acetate-grafted ethylene-vinyl acetate copolymer wax (manufactured according to DD 293 125 A5, total content of vinyl acetate 38 masses, molar mass weight average 6400 g / mol, vinyl acetate content of the non-grafted ethylene-vinyl acetate copolymer wax 32 masses!) and 60 masses! a non-grafted ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32 pounds, weight average molar mass 4400 g / mol.
4.1.3 Additivkomponente b)4.1.3 Additive component b)
Gemisch C3-oxyalkylverbrückter ungesättigter Cι8-C4- Carbonsäuren, Veresterungsgrad 92 Moll, Gehalt an Ciβ- ungesättigten Fettsäuren 32 Massel, Gehalt an C22- ungesättigten Fettsäuren 48 Massel, Jodzahl 96Mixture of C 3 -oxyalkyl-bridged unsaturated C 8 -C 4 carboxylic acids, degree of esterification 92 minor, content of Ciβ unsaturated fatty acids 32 masses, content of C 22 unsaturated fatty acids 48 masses, iodine number 96
4.1.4 Weitere Additivkomponenten Polyethylenglycolmonomethylether, Molmassen-Zahlenmittel 15004.1.4 Other additive components polyethylene glycol monomethyl ether, number average molecular weight 1500
Laurylacrylat-Ethylacrylat-Copolymer (Molverhältnis 3 : 1)Lauryl acrylate-ethyl acrylate copolymer (3: 1 molar ratio)
4.2 Herstellung der Additivkomponenten enthaltenden Lösungen in Mineralöl-Mitteldestillaten4.2 Preparation of the solutions containing additive components in mineral oil middle distillates
In einen Rührbehälter, der 20 kg einer 6Öligen Lösung der Additivkomponente a) in Cs-Cg-Diesel-Aromatenfraktion enthält, werden 10 kg einer 40!igen Lösung der Additiv- komponente b) in Cs-Cg-Diesel-Aromatenfraktion und als weitere Additivkomponenten 1,0 kg Polyethylenglycolmono- methylether und 6,2 kg einer 2Öligen Lösung von Laurylac- rylat-Ethylacrylat-Copolymer in Toluen eingetragen, 90 min gerührt, und die Mischung in einen Vorratstank überführt .10 kg of a 40% solution of additive component b) in Cs-Cg-diesel aromatic fraction and as further additive components are placed in a stirred container which contains 20 kg of a 6-oil solution of additive component a) in Cs-Cg-diesel aromatic fraction 1.0 kg of polyethylene glycol monomethyl ether and 6.2 kg of a 2-oil solution of lauryl acrylate-ethyl acrylate copolymer in toluene, 90 min stirred, and the mixture was transferred to a storage tank.
4.3 Herstellung der Rezeptur aus Mineralöl4.3 Production of the recipe from mineral oil
In einen Produktstrom nichtadditiviertes Heizöl Charge 030218 bei 800 kg/min wird mit 0,28 kg/min die Additivlösung nach 4.2 eingespritzt und in einen Lagertank überführt .The additive solution according to 4.2 is injected into a product stream of non-additized heating oil batch 030218 at 800 kg / min at 0.28 kg / min and transferred to a storage tank.
Die Ausprüfung der Kältebeständigkeit der Mineralölrezeptur ergibt einen CFPP-Wert von -15°C.Testing the cold resistance of the mineral oil formulation gives a CFPP value of -15 ° C.
Wird unter gleichen Bedingungen eine Mineralölrezeptur hergestellt, die ausschließlich das nichtgepfropfte Copo- lymerwachs als Additiv enthält, so beträgt der CFPP-Wert -1°C.If a mineral oil recipe is produced under the same conditions that contains only the non-grafted copolymer wax as an additive, the CFPP value is -1 ° C.
Beispiel 5Example 5
5.1 Ausgangsprodukte5.1 Starting products
5.1.1 Unadditivierter Diesel Charge : 16080601 Test DK 1 Charakterisierung :5.1.1 Unadditized Diesel Charge: 16080601 Test DK 1 Characterization:
Cloud Point (CP) : +6 °C ;Cloud Point (CP): +6 ° C;
Cold Filter Plugging Point (CFPP) : +2 °CCold filter plugging point (CFPP): +2 ° C
Siedeanalyse :Boiling analysis:
Destillierte Menge (Vol.-!) / Temperatur (°C)Distilled quantity (Vol.-!) / Temperature (° C)
IBP 10 20 30 40 50 60 70 80 90 FBPIBP 10 20 30 40 50 60 70 80 90 FBP
189 243 259 271 281 292 303 317 334 357 385 5.1.2 Additivkomponente a)189 243 259 271 281 292 303 317 334 357 385 5.1.2 Additive component a)
Mischung aus 60 Masse! eines Vinylacetatgepfropften E- thylen-Vinylacetat-Copolymerwachses (hergestellt nach DD 293 125 A5, Gesamtgehalt an Vinylacetat 45 Massel, Molmassen-Gewichtsmittel 3800 g/mol, Vinylacetatgehalt des nichtgepfropften Ethylen-Vinylacetat-Copolymerwachses 32 Masse!) und 40 Masse! eines nichtgepfropften Ethylen- Vinylacetat-Copolymerwachses (Hersteller LEUNA Polymer GmbH, Vinylacetatgehalt 30,1 Massel, Molmassen-Zahlenmittel 1920 g/mol) .Mixture of 60 mass! a vinyl acetate-grafted ethylene-vinyl acetate copolymer wax (manufactured according to DD 293 125 A5, total vinyl acetate content 45 brass, molar mass weight average 3800 g / mol, vinyl acetate content of the non-grafted ethylene-vinyl acetate copolymer wax 32 mass!) and 40 mass! a non-grafted ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 30.1 pounds, number average molecular weight 1920 g / mol).
5.1.3 Additivkomponente b) Gemisch C3-oxyalkylverbrückter ungesättigter Cι8-C24- Carbonsäuren, Veresterungsgrad 92 Moll, Gehalt an Cι8- ungesättigten Fettsäuren 32 Massel, Gehalt an C2 _ ungesättigten Fettsäuren 48 Massel, Jodzahl 965.1.3 Additive component b) mixture of C 3 -oxyalkyl-bridged unsaturated C 8 -C 24 carboxylic acids, degree of esterification 92 minor, content of C 8 unsaturated fatty acids 32 masses, content of C 2 _ unsaturated fatty acids 48 masses, iodine number 96
5.1.4 Additivkomponente c)5.1.4 Additive component c)
Styrol-Maleinsäureanhydrid-Copolymer, mit Cι6-Cι8-Fettamin teilimidisiert, Molmassenzahlenmittel 26500 g/mol, Säurezahl 8,2Styrene-maleic anhydride copolymer, partially imidized with -C 6 -C 8 fatty amine, number average molecular weight 26500 g / mol, acid number 8.2
5.1.5 Weitere Additivkomponente5.1.5 Other additive components
Octadecylacrylat-Ethylacrylat-Copolymer (Molverhältnis 4 : 1, Molmassen-Zahlenmittel 13500) 5.2 Herstellung der Additivkomponenten enthaltenden Lösungen in Mineralöl-MitteldestillatenOctadecyl acrylate-ethyl acrylate copolymer (4: 1 molar ratio, number average molecular weight 13500) 5.2 Preparation of the solutions containing additive components in mineral oil middle distillates
In einem Rührbehälter werden 10 kg einer 40!igen Lösung der Additivkomponente c) in Cs-Cg-Diesel-Aromatenfrak- tion, 20 kg einer 5Öligen Lösung der Additivkomponente a) in einem aromatischen Kohlenwasserstoffgemisch, 10 kg der Additivkomponente b) und 8 kg einer 2Öligen Lösung der weiteren Additivkomponente Octadecylacrylat-Ethylacrylat- Copolymer in Toluen 90 min bei 65°C gemischt, und die Mischung in einen Vorratstank überführt .10 kg of a 40% solution of the additive component c) in a Cs-Cg-Diesel aromatic fraction, 20 kg of a 5-oil solution of the additive component a) in an aromatic hydrocarbon mixture, 10 kg of the additive component b) and 8 kg of a 2-oily solution of the further additive component octadecyl acrylate-ethyl acrylate copolymer in toluene mixed for 90 min at 65 ° C, and the mixture is transferred to a storage tank.
5.3 Herstellung der Mineralölrezeptur5.3 Production of the mineral oil formulation
In einen Produktstrom nichtadditiviertem Diesel Charge 16080601 bei 800 kg/min wird mit 0,48 kg/min die Additivlösung nach 5.2 eingespritzt und in einen Lagertank überführt . Die Ausprüfung der Kältebeständigkeit der Mineralölrezep- tur ergibt einen CFPP-Wert von -17°C. Der CP-Wert des Kurzzeitsediment-Tests beträgt +6°C. Der SEDAB Filtrations-Test gilt als bestanden (500 ml in 75 s) . Wird unter gleichen Bedingungen eine Mineralölrezeptur hergestellt, die ausschließlich das nichtgepfropfte Copo- lymerwachs als Additiv enthält, so beträgt der CFPP-Wert -3°C. Der CP-Wert des Kurzzeitsediment-Tests beträgt +10°C. Der SEDAB Filtrations-Test gilt als nicht bestanden (468 ml in >120 s) . Beispiel 6The additive solution according to 5.2 is injected into a product stream of non-additized diesel batch 16080601 at 800 kg / min at 0.48 kg / min and transferred to a storage tank. Testing the cold resistance of the mineral oil formulation gives a CFPP value of -17 ° C. The CP value of the short-term sediment test is + 6 ° C. The SEDAB filtration test is passed (500 ml in 75 s). If a mineral oil formulation is produced under the same conditions that contains only the non-grafted copolymer wax as an additive, the CFPP value is -3 ° C. The CP value of the short-term sediment test is + 10 ° C. The SEDAB filtration test is considered failed (468 ml in> 120 s). Example 6
6.1 Ausgangsprodukte6.1 Starting products
6.1.1 Unadditivierter Diesel Charge : 030210 Test DK 2 Charakterisierung : Cloud Point (CP) : +7 °C ;6.1.1 Unadditized Diesel Charge: 030210 Test DK 2 Characterization: Cloud Point (CP): +7 ° C;
Cold Filter Plugging Point (CFPP) : +2 °C Siedeanalyse :Cold filter plugging point (CFPP): +2 ° C boiling analysis:
Destillierte Menge (Vol.-!) / Temperatur (°C)Distilled quantity (Vol.-!) / Temperature (° C)
IBP 10 20 30 40 50 60 70 80 90 FBPIBP 10 20 30 40 50 60 70 80 90 FBP
235 266 279 291 301 310 320 337 342 357 374235 266 279 291 301 310 320 337 342 357 374
6.1.2 Additivkomponente a)6.1.2 Additive component a)
Mischung aus 50 Masse! eines teilverseiften Ethylen- Vinylacetat-Copolymerwachses (Molmassen-Gewichtsmittel 1650 g/mol, Vinylacetatgehalt des nichtverseiften E- thylen-Vinylacetat-Copolymerwachses 32 Massel, Versei- fungsgrad 15 Mol!) und 50 Masse! eines nichtverseiften Ethylen-Vinylacetat-Copolymerwachses (Hersteller LEUNA Polymer GmbH, Vinylacetatgehalt 32 Massel, Molmassen- Zahlenmittel 2015 g/mol.Mix of 50 mass! a partially saponified ethylene-vinyl acetate copolymer wax (weight average molecular weight 1650 g / mol, vinyl acetate content of the unsaponified ethylene-vinyl acetate copolymer wax 32 pounds, degree of saponification 15 moles!) and 50 masses! a non-saponified ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32 brass, molar mass number average 2015 g / mol.
6.1.3 Additivkomponente c)6.1.3 Additive component c)
Octadecen-Maleinsäureanhydrid-Copolymer, mit Ci6-Cι8- Fettamin teilimidisiert, Säurezahl 40, Molmassen-Zahlen- mittel 4200 g/mol,Octadecen-maleic anhydride copolymer, partially imidized with Ci 6 -Cι 8 - fatty amine, acid number 40, number average molar mass 4200 g / mol,
6.1.4 Weitere Additivkomponenten Triester von Pentaerythrit mit Stearinsäure Dipropylenglycolmonopropylether6.1.4 Other additive components Triester of pentaerythritol with stearic acid Dipropylenglycolmonopropylether
6.2 Herstellung der Additivkomponenten enthaltenden Lösungen in Mineralöl-Mitteldestillaten6.2 Preparation of the solutions containing additive components in mineral oil middle distillates
In einem Rührbehälter werden 10 kg einer 40!igen Lösung der Additivkomponente c) in C8-C9-Diesel-Aromatenfrak- tion, 20 kg einer 60!igen Lösung der Additivkomponente a) in C8-Cg-Diesel-Aromatenfraktion, 10 kg der weiteren Ad- ditivkomponente Triester von Pentaerythrit mit Stearinsäure und 1 kg der weiteren Additivkomponente Dipropy- lenglycolmonopropylether 90 min bei 65°C gemischt, und die Mischung in einen Vorratstank überführt.10 kg of a 40% solution of the additive component c) in a C 8 -C 9 diesel aromatic fraction, 20 kg of a 60% solution of the additive component a) in a C 8 -Cg diesel aromatic fraction, 10 kg of the other additive component triester of pentaerythritol mixed with stearic acid and 1 kg of the further additive component dipropylene glycol monopropyl ether for 90 min at 65 ° C., and the mixture was transferred to a storage tank.
6.3 Herstellung der Mineralölrezeptur6.3 Production of the mineral oil formulation
In einen Produktstrom nichtadditiviertem Diesel Charge 030210 bei 800 kg/min wird mit 0,24 kg/min die Additivlösung nach 6.2 eingespritzt und in einen Lagertank über- führt .The additive solution according to 6.2 is injected into a product stream of non-additized Diesel Charge 030210 at 800 kg / min at 0.24 kg / min and transferred to a storage tank.
Die Ausprüfung der Kältebeständigkeit der Mineralölrezeptur ergibt einen CFPP-Wert von -7°C. Der CP-Wert des Kurzzeitsediment-Tests beträgt +8°C. Der SEDAB Filtrations-Test gilt als bestanden (500 ml in 82 s) . Wird unter gleichen Bedingungen eine Mineralölrezeptur hergestellt, die ausschließlich das nichtverseifte Copo- lymerwachs als Additiv enthält, so beträgt der CFPP-Wert -5°C. Der CP-Wert des Kurzzeitsediment-Tests beträgt +12°C. Der SEDAB Filtrations-Test gilt als nicht bestan- den (468 ml in >120 s) . Beispiel 7Testing the cold resistance of the mineral oil formulation gives a CFPP value of -7 ° C. The CP value of the short-term sediment test is + 8 ° C. The SEDAB filtration test is passed (500 ml in 82 s). If a mineral oil formulation is produced under the same conditions that contains only the non-saponified copolymer wax as an additive, the CFPP value is -5 ° C. The CP value of the short-term sediment test is + 12 ° C. The SEDAB filtration test is considered failed (468 ml in> 120 s). Example 7
7.1 Ausgangsprodukte7.1 Starting products
7.1.1 Unadditiviertes Heizöl Charge : 030225 Test HEL 1 Charakterisierung : Cloud Point (CP) : +1 °C ;7.1.1 Unadditized heating oil batch: 030225 test HEL 1 characterization: Cloud Point (CP): +1 ° C;
Cold Filter Plugging Point (CFPP) : -1 °C Siedeanalyse :Cold Filter Plugging Point (CFPP): -1 ° C Boiling analysis:
Destillierte Menge (Vol.-!) / Temperatur (°C)Distilled quantity (Vol.-!) / Temperature (° C)
IBP 10 20 30 40 50 60 70 80 90 FBPIBP 10 20 30 40 50 60 70 80 90 FBP
165 196 213 230 249 269 290 310 327 344 363165 196 213 230 249 269 290 310 327 344 363
7.1.2 Additivkomponente a)7.1.2 Additive component a)
Mischung aus 40 Masse! eines oxidierten Ethylen-Vinylace- tat-Copolymerwachses (Molmassen-Zahlenmittel 950 g/mol, Säurezahl 18 mg KOH/g, OH-Zahl 70 mg KOH/g) und 60 Masse! eines nichtoxidierten Ethylen-Vinylacetat-Copolymer- wachses (Hersteller LEUNA Polymer GmbH, Vinylacetatgehalt 32 Massel, Molmassen-Gewichtsmittel 4400 g/mol.Mixture of 40 mass! an oxidized ethylene-vinyl acetate copolymer wax (number average molecular weight 950 g / mol, acid number 18 mg KOH / g, OH number 70 mg KOH / g) and 60 mass! of an unoxidized ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32 pounds, weight average molar mass 4400 g / mol.
7.1.3 Additivkomponente b) : Diester von Propylen- glycol mit Ölsäure7.1.3 Additive component b): diester of propylene glycol with oleic acid
7.1.4 Additivkomponente c)7.1.4 Additive component c)
α-Methylstyrol-Maleinsäureanhydrid-Copolymer, mit Oleyla- min teilimidisiert, Molmassenzahlenmittel 16500 g/mol, Säurezahl 15 7.2 Herstellung der Additivkomponenten enthaltenden Lösungen in Mineralöl-Mitteldestillatenα-methylstyrene-maleic anhydride copolymer, partially imidized with olymine, molecular weight average 16500 g / mol, acid number 15 7.2 Preparation of the solutions containing additive components in mineral oil middle distillates
In einem Rührbehälter werden 25 kg einer 4Öligen der Additivkomponente c) in Cs-Cg-Diesel-Aromatenfraktion, 50 kg einer 60!igen Lösung der Additivkomponente a) in Cs- Cg-Diesel-Aromatenfraktion und 25 kg der Additivkomponente b) 90 min bei 65°C gemischt, und die Mischung in einen Vorratstank überführt .25 kg of a 4-oil of the additive component c) in Cs-Cg-diesel-aromatic fraction, 50 kg of a 60% solution of the additive component a) in Cs-Cg-diesel-aromatic fraction and 25 kg of the additive component b) are added in a stirred tank for 90 minutes 65 ° C mixed, and the mixture is transferred to a storage tank.
7.3 Herstellung der Mineralölrezeptur7.3 Production of the mineral oil formulation
In einen Produktstrom nichtadditiviertem Diesel Charge 030225 bei 800 kg/min wird mit 0,24 kg/min die Additivlösung nach 7.2 eingespritzt und in einen Lagertank überführt .The additive solution according to 7.2 is injected into a product stream of non-additized Diesel Charge 030225 at 800 kg / min at 0.24 kg / min and transferred to a storage tank.
Die Ausprüfung der Kältebeständigkeit der Mineralölrezep- tur ergibt einen CFPP-Wert von -15°C.Testing the cold resistance of the mineral oil formulation gives a CFPP value of -15 ° C.
Wird unter gleichen Bedingungen eine Mineralölrezeptur hergestellt, die ausschließlich das nichtverseifte Copo- lymerwachs als Additiv enthält, so beträgt der CFPP-Wert -13°C.If a mineral oil formulation is produced under the same conditions that contains only the unsaponified copolymer wax as an additive, the CFPP value is -13 ° C.
Beispiel 8Example 8
8.1 Ausgangsprodukte8.1 Base products
8.1.1 Unadditivierter Diesel8.1.1 Unadditized Diesel
Charge : 16080601 Test DK 1 Charakterisierung :Batch: 16080601 test DK 1 Characterization:
Cloud Point (CP) : +6 °C ;Cloud Point (CP): +6 ° C;
Cold Filter Plugging Point (CFPP) : +2 °CCold filter plugging point (CFPP): +2 ° C
Siedeanalyse :Boiling analysis:
Destillierte Menge (Vol.-!) / Temperatur (°C)Distilled quantity (Vol.-!) / Temperature (° C)
IBP 10 20 30 40 50 60 70 80 90 FBPIBP 10 20 30 40 50 60 70 80 90 FBP
189 243 259 271 281 292 303 317 334 357 385189 243 259 271 281 292 303 317 334 357 385
8.1.2 Additivkomponente a)8.1.2 Additive component a)
Mischung aus 40 Masse! eines Vinylacetatgepfropften E- thylen-Vinylacetat-Copolymerwachses (hergestellt nach DD 293 125 A5, Gesamtgehalt an Vinylacetat 38 Massel, Molmassen-Gewichtsmittel 3900 g/mol, Vinylacetatgehalt des nichtgepfropften Ethylen-Vinylacetat-Copolymerwachses 32 Masse!) und 60 Masse! eines nichtgepfropften Ethylen- Vinylacetat-Copolymerwachses (Hersteller LEUNA Polymer GmbH, Vinylacetatgehalt 33 Massel, Molmassen-Gewichtsmittel 2300 g/mol.Mixture of 40 mass! a vinyl acetate-grafted ethylene-vinyl acetate copolymer wax (manufactured according to DD 293 125 A5, total content of vinyl acetate 38 masses, molar mass weight average 3900 g / mol, vinyl acetate content of the non-grafted ethylene-vinyl acetate copolymer wax 32 masses!) and 60 masses! a non-grafted ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 33 pounds, weight average molar mass 2300 g / mol.
8.1.3 Additivkomponente c) -Methylstyrol-Maleinsäureanhydrid-Copolymer, mit Cι2-Cι4- Cocosamin teilimidisiert, Mol assenzahlenmittel 11000 g/mol, Säurezahl 25, Schmelzpunkt 63°C8.1.3 Additive component c) -methylstyrene-maleic anhydride copolymer, partially imidized with C 2 -C 4 - cocosamine, molar number average 11000 g / mol, acid number 25, melting point 63 ° C.
8.1.4 Weitere Additivkomponenten8.1.4 Other additive components
Pentaethylenhexamin-1 , 2-diaminobutanol Polypropylenglycol Molmasse 1500 8.2 Herstellung der Additivkomponenten enthaltenden Lösungen in Mineralöl-MitteldestillatenPentaethylene hexamine-1,2-diaminobutanol polypropylene glycol molecular weight 1500 8.2 Preparation of the solutions containing additive components in mineral oil middle distillates
In einem Rührbehälter werden 25 kg einer 4Öligen Lösung der Additivkomponente c) in Cs-Cg-Diesel-Aromatenfraktion, 50 kg einer 50!igen Lösung der Additivkomponente a) in einem aromatischen Kohlenwasserstoffgemiseh, 4 kg der weiteren Additivkomponente Pentaethylenhexamin-1, 2- diaminobutanol und 3 kg der weiteren Additivkomponente Polypropylengly- col Molmasse 1500 eingetragen, 90 min bei 65°C gemischt, und die Mischung in einen Vorratstank überführt.25 kg of a 4-oil solution of the additive component c) in a Cs-Cg-Diesel aromatic fraction, 50 kg of a 50% solution of the additive component a) in an aromatic hydrocarbon mixture, 4 kg of the further additive component pentaethylenehexamine-1,2-diaminobutanol are placed in a stirred container and 3 kg of the further additive component polypropylene glycol molecular weight 1500 were added, mixed for 90 min at 65 ° C., and the mixture was transferred to a storage tank.
8.3 Herstellung der Mineralölrezeptur8.3 Production of the mineral oil formulation
In einen Produktstrom nichtadditiviertem Diesel Charge 16080601 bei 800 kg/min wird mit 0,48 kg/min die Addi- tivlösung nach 8.2 eingespritzt und in einen Lagertank überführt .The additive solution according to 8.2 is injected into a product stream of non-additized diesel batch 16080601 at 800 kg / min at 0.48 kg / min and transferred to a storage tank.
Die Ausprüfung der Kältebeständigkeit der Mineralölrezeptur ergibt einen CFPP-Wert von -13°C.Testing the cold resistance of the mineral oil formulation gives a CFPP value of -13 ° C.
Wird unter gleichen Bedingungen eine Mineralölrezeptur hergestellt, die ausschließlich das nichtgepfropfte Copo- lymerwachs als Additiv enthält, so beträgt der CFPP-Wert -3°C. If a mineral oil formulation is produced under the same conditions that contains only the non-grafted copolymer wax as an additive, the CFPP value is -3 ° C.

Claims

Patentansprüche claims
1. Additivmischung als Bestandteil einer Rezeptur aus Mineralöl als Hauptkomponente und geringen Anteilen einer Additivmischung, dadurch gekennzeichnet, dass die Additivmischung die Additivkomponenten a) durch polare Gruppen modifizierte Ethylen- Vinylester-Copolymere mit Molmassengewichtsmitteln von 3000 bis 50000 und einem Ethylenanteil von 50 bis 90 Massel, und b) C2-C6-oxyalkylverbrückte Cχ2-C4o-Monocarbonsäuren, und/oder c) partiell und/oder vollständig imidisierte Copolymere aus ungesättigten C4-C20- Dicarbonsäureanhydri- den und Vinylaromaten und/oder C2-C36-α-01efinen enthalten, wobei der Gehalt der Additivmischung im Mineralöl 0,005 bis 1 Masse! und das Masseverhältnis der Addi- tivkomponenten a/b oder a/c oder a/ (b+c) jeweils 10 : 90 bis 90 : 10 beträgt.1. Additive mixture as part of a recipe made from mineral oil as the main component and small proportions of an additive mixture, characterized in that the additive mixture comprises the additive components a) ethylene-vinyl ester copolymers modified by polar groups with a weight average molecular weight of 3,000 to 50,000 and an ethylene content of 50 to 90 pigments , and b) C 2 -C 6 -oxyalkyl-bridged Cχ 2 -C 4 o-monocarboxylic acids, and / or c) partially and / or completely imidized copolymers of unsaturated C 4 -C 20 dicarboxylic acid anhydrides and vinyl aromatics and / or C 2 -C 36 -α-01efinen contain, the content of the additive mixture in the mineral oil 0.005 to 1 mass! and the mass ratio of the additive components a / b or a / c or a / (b + c) is in each case 10:90 to 90:10.
2. Additivmischung nach Anspruch 1, dadurch gekenn- zeichnet, dass die durch polare Gruppen modifizierten Ethylen-Vinylester-Copolymere oxidierte Ethylen- Vinylacetat-Copolymere mit Molmassen-Zahlenmitteln von 800 bis 5000, Säurezahlen von 2 bis 40 mg KOH/g und OH-Zahlen von 20 bis 150 mg KOH/g, oder teilver- seifte Ethylen-Vinylacetat-Copolymere mit Molmassen- Zahlenmitteln von 800 bis 5000 sind, bei denen 5 bis 30 Mol! der Vinylacetateinheiten verseift vorliegen, oder Halbacetale von Ethylen-Vinylester-Vinylal- kohol-Copolymeren mit Butyraldehyd, sind.2. Additive mixture according to claim 1, characterized in that the ethylene-vinyl acetate copolymers modified by polar groups are oxidized ethylene-vinyl acetate copolymers with number average molecular weights of 800 to 5000, acid numbers of 2 to 40 mg KOH / g and OH- Numbers from 20 to 150 mg KOH / g, or partially saponified ethylene-vinyl acetate copolymers with number average molecular weights of 800 to 5000, in which 5 to 30 moles are! the vinyl acetate units are saponified, or hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyraldehyde.
3. Additivmischung nach Anspruch 1, dadurch gekennzeichnet, dass die durch polare Gruppen modifizierten Ethylen-Vinylester-Copolymere mit 6 bis 20 Masse! polaren ungesättigten Monomeren vom Typ Vinylester, (Meth) -acrylester und/oder Vinylether gepfropfte Ethylen-Vinylester-Copolymere sind.3. Additive mixture according to claim 1, characterized in that the ethylene-vinyl ester copolymers modified by polar groups with 6 to 20 mass! polar unsaturated monomers of the vinyl ester type, (meth) acrylic ester and / or vinyl ether are grafted ethylene-vinyl ester copolymers.
4. Additivmischung nach Anspruch 3, dadurch gekennzeichnet, dass die durch polare Gruppen modifizierten Ethylen-Vinylester-Copolymere mit Vinylacetat gepfropfte Ethylen-Vinylacetat-Copolymere mit Mol- massenzahlenmitteln von 800 bis 5000 und einem Ge- samtvinylacetatgehalt von 20 bis 60 Masse! sind, wobei der Vinylacetatgehalt der Copolymerrückgratkette 10 bis 40 Masse! und der Anteil der aufgepfropften Vinylacetat-Seitenketten 10 bis 20 Masse! beträgt.4. Additive mixture according to claim 3, characterized in that the ethylene-vinyl ester copolymers modified by polar groups are grafted with vinyl acetate and ethylene-vinyl acetate copolymers with molar mass numbers of 800 to 5000 and a total vinyl acetate content of 20 to 60 mass! are, where the vinyl acetate content of the copolymer backbone chain 10 to 40 mass! and the proportion of grafted vinyl acetate side chains 10 to 20 mass! is.
5. Additivmischung nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die C2-Cδ- oxyalkylverbrückten Cι2-C4o-Monocarbonsäu-ren Ester von ungesättigten Ci6-C2-Monocarbonsäuren mit C3-C4- Polyalkoholen sind, wobei der Anteil von C22- Monocarbonsäuren, bezogen auf die Gesamtmasse der Ci6-C24-Monocarbonsäuren, 45 bis 52 Masse! beträgt.5. Additive mixture according to one or more of claims 1 to 4, characterized in that the C 2 -C δ - oxyalkyl bridged C 2 -C 4 o-monocarboxylic acid esters of unsaturated Ci 6 -C 2 monocarboxylic acids with C 3 -C 4 - polyalcohols, the proportion of C 22 - monocarboxylic acids, based on the total mass of the Ci 6 -C 24 monocarboxylic acids, 45 to 52 mass! is.
6. Additivmischung nach einem oder mehreren der Ansprü- ehe 1 bis 5, dadurch gekennzeichnet, dass die partiell imidisierten Copolymere aus ungesättigten Di- carbonsäureanhydriden und Vinylaromaten partiell mit C6-C24- onoalkyl-aminen imidisierte Maleinsäurean- hydrid- -Methylstyrol-Copolymere sind, bei denen das Molverhältnis Anhydridgruppen im Copolymer / gebundenes C6-C4-Monoalkylamin im Copolymer 8 : 1 bis 1,3 : 1 beträgt .6. Additive mixture according to one or more of the before Ansprü- 1 to 5, characterized in that the partially imidized copolymers of unsaturated carboxylic di- and vinylaromatics partially with C 6 -C 24 - amines onoalkyl-imidized maleic are hydride-methylstyrene copolymers in which the molar ratio of anhydride groups in the copolymer / bound C 6 -C 4 -monoalkylamine in the copolymer is 8: 1 to 1.3: 1.
7. Rezeptur aus Mineralöl nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Mineralöle Rohöle oder Brennstofföle aus einem Mitteldestillat mit einem Schwefelgehalt unter 0,05 Massel, bevorzugt Heizöle, Gasöle oder Dieselöle, sind.7. Recipe from mineral oil according to one or more of claims 1 to 6, characterized in that the mineral oils are crude oils or fuel oils from a middle distillate with a sulfur content below 0.05 ingots, preferably heating oils, gas oils or diesel oils.
8. Rezeptur aus Mineralöl nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Mineralöl insgesamt 0 bis 200 Massel, bezogen auf die Summe der Additivkomponenten a) und b) oder a) und c) oder a) , b) und c) , weitere Additivkomponenten vom Typ Fettsäuregemische, polare StickstoffVerbindungen, bevorzugt Polyamine, Ethera ine, Aminoal- kohole, Aminsalze, Amide oder Imide von mehrwertigen Carbonsäuren; C7-C30-Alkohole, Polyalkylenglyco- le, Ester oder Ether von Polyoxyalkylenverbindungen, nichtmodifizierte Ethylen-Vinylester-Copolymere, Kohlenwasserstoffpolymere, Alkylphenol-Aldehyd-Copo- lymere, aromatische Verbindungen mit C8-Cι0o-Alkyl- substituenten, carboxylierte Polyamine, Detergen- tien, Korrosionsinhibitoren, Demulgatoren, Metallde- saktivatoren, Cetanverbesserer, Entschäumer und/oder Cosolventien enthält.8. Recipe from mineral oil according to one or more of claims 1 to 7, characterized in that the mineral oil in total 0 to 200 ingots, based on the sum of the additive components a) and b) or a) and c) or a), b) and c), further additive components of the fatty acid mixture type, polar nitrogen compounds, preferably polyamines, ether amines, amino alcohols, amine salts, amides or imides of polyvalent carboxylic acids; C 7 -C 30 alcohols, Polyalkylenglyco- le, substituents esters or ethers of polyoxyalkylene compounds, unmodified ethylene-Vinylester copolymers, hydrocarbon polymers, alkylphenol-aldehyde copolymers, aromatic compounds having C 8 -Cι 0 o alkyl, carboxylated Contains polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane improvers, defoamers and / or cosolvents.
Verfahren zur Herstellung von Rezepturen aus Mineralöl als Hauptkomponente und geringen Anteilen ei- ner Additivmischung, dadurch gekennzeichnet, dass Rezepturen, die die Additivkomponenten a) durch polare Gruppen modifizierte Ethylen- Vinylester-Copolymere mit Molmassengewichtsmitteln von 3000 bis 50000 und einem Ethylenanteil von 50 bis 90 Massel, und b) C2-C6-oxyalkylverbrückte Cι2-C4o-Monocarbonsäuren, und/oder c) partiell und/oder vollständig imidisierte Copoly- mere aus ungesättigten C4-C2o-Dicarbonsäureanhydriden und Vinylaromaten und/oder C2-C36- -0lefinen enthalten, wobei der Gehalt der Additivmischung im Mineralöl 0,005 bis 1 Masse! und das Masseverhältnis der Addi- tivkomponenten a/b oder a/c oder a/ (b+c) 10 : 90 bis 90 : 10 beträgt, nach einem Vorhomogenisierungsverfahren hergestellt werden, bei demProcess for the production of formulations from mineral oil as the main component and small proportions of ner additive mixture, characterized in that formulations containing the additive components a) modified by polar groups, ethylene-vinyl ester copolymers with weight-average molecular weights of 3000 to 50,000 and an ethylene content of 50 to 90 ingots, and b) C 2 -C 6 -oxyalkyl-bridged Cι 2 -C 4 o-monocarboxylic acids, and / or c) partially and / or completely imidized copolymers of unsaturated C 4 -C 2 o-dicarboxylic acid anhydrides and vinyl aromatics and / or C 2 -C 36 - -0-olefins, the content of Additive mixture in mineral oil 0.005 to 1 mass! and the mass ratio of the additive components a / b or a / c or a / (b + c) is 10:90 to 90:10, are produced by a pre-homogenization process in which
- in der ersten Verfahrensstufe 1 bis 60 Masse! Ad- ditivkomponenten enthaltende Lösungen in Mineralöl- Mitteldestillaten bei 20 bis 90°C hergestellt werden, und- in the first process stage 1 to 60 mass! Solutions containing additive components are prepared in mineral oil middle distillates at 20 to 90 ° C, and
- in der zweiten Verfahrensstufe die Additivkompo- nenten enthaltenden Lösungen mit dem Mineralöl als- In the second stage of the process, the solutions containing the additive components with the mineral oil as
Hauptkomponente homogenisiert werden, wobei dem Mineralöl insgesamt 0 bis 200 Massel, bezogen auf die Summe der Additivkomponenten a) und b) oder a) und c) oder a) , b) und c) , weitere Addi- tivkomponenten in der ersten und/oder zweiten Verfahrensstufe zugesetzt werden. Main component are homogenized, the mineral oil totaling 0 to 200 pounds, based on the sum of additive components a) and b) or a) and c) or a), b) and c), further additive components in the first and / or second stage of the process can be added.
0. Verwendung von Rezepturen nach einem oder mehreren der Ansprüche 1 bis 9 als bei niedrigen Temperaturen zu transportierende fließfähige Medien und als Mineralölkraftstoff hoher Schmierwirkung und Fliessfähigkeit. 0. Use of recipes according to one or more of claims 1 to 9 as flowable media to be transported at low temperatures and as a mineral oil fuel with high lubrication and flowability.
PCT/DE2004/002314 2003-10-22 2004-10-15 Additive mixture as component of a mineral oil composition WO2005040315A1 (en)

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KR1020067007765A KR100749220B1 (en) 2003-10-22 2004-10-15 Additive Mixture as Component of a Mineral Oil Composition
CA002542935A CA2542935C (en) 2003-10-22 2004-10-15 Additive mixture as component of a mineral oil composition
EP04790006A EP1685216B1 (en) 2003-10-22 2004-10-15 Composition of mineral oil and an additive mixture
ES04790006T ES2402928T3 (en) 2003-10-22 2004-10-15 Composition from mineral oil and a mixture of additives
EA200600804A EA011358B1 (en) 2003-10-22 2004-10-15 Mineral oil composition comprising additive mixture, additive mixture as components of mineral oil composition, a method for producing thereof and use thereof
US10/577,006 US7776801B2 (en) 2003-10-22 2004-10-15 Additive mixture as component of a mineral oil composition
JP2006535936A JP4991302B2 (en) 2003-10-22 2004-10-15 Additive mixture as a component of mineral oil composition

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US20070219100A1 (en) 2007-09-20
KR20060090252A (en) 2006-08-10
US7776801B2 (en) 2010-08-17
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